CN104145219A

CN104145219A - Magenta toner containing compound having azo skeleton

Info

Publication number: CN104145219A
Application number: CN201380011557.9A
Authority: CN
Inventors: 渡部大辉; 丰田隆之; 村井康亮; 长谷川和香; 长谷川由纪; 河村政志; 关真范; 西浦千晶; 增田彩乃; 广濑雅史
Original assignee: Canon Inc
Current assignee: Canon Inc
Priority date: 2012-02-29
Filing date: 2013-02-27
Publication date: 2014-11-12
Also published as: RU2014138980A; JP2013210629A; EP2820481A4; EP2820481A1; WO2013129694A1; KR20140129218A; US20150004539A1

Abstract

An object of the present invention is to provide a magenta toner having improved dispersibility of a magenta pigment in a binder resin and a high coloring ability, enabling suppression of fogging, and having high transfer efficiency. The object can be attained by a toner including toner particles containing a binder resin, a compound having an azo skeleton bound to a polymeric portion, and a magenta pigment as a colorant.

Description

The magenta toner that comprises the compound with azo skeleton

Technical field

The present invention relates to comprise the compound with azo skeleton structure as the spreading agent of magenta pigment and for the magenta toner of electrofax, electrostatic recording, xeroprinting or toner injection record.

Background technology

The magenta pigment that is typically used as the colorant of magenta toner has small particle diameter and is difficult to disperses.The insufficient dispersion of magenta pigment in toner-particle causes the colouring power of toner to decline.Further, the chargeding performance of toner is changed significantly by the change of the environment such as temperature and humidity.In addition haze, " " thus the non-image part development at image by toner easily produced.

As the technology that magenta toner is disperseed in toner-particle, for example, PTL 1 discloses a kind of method, thereby wherein specific macromolecule dispersing agent is used in combination the dispersiveness of raising magenta pigment with magenta pigment, and improves coloring and the charging property of toner.

In addition, PTL 2 discloses a kind of pigment derivative and macromolecule dispersing agent of wherein using, the method that the coloured material in toner disperses well.

Further, PTL 3 discloses a kind of method that wherein quinoline Azone is covalently bonded to the pigment dispersing agent of polymkeric substance.

Meanwhile, in order to improve band electrical stability and " hazing " of magenta toner, PTL 4 has proposed a kind of method of wherein using diketo pyrroles (diketopyrrole) pigment to replace quinoline Azone pigment.

Reference listing

Patent documentation

PTL 1: Japanese Patent Application Laid-Open No.2006-30760

PTL 2: Japanese Patent Application Laid-Open No.H11-231572

PTL 3: Japanese Patent Application Laid-Open No.2003-202697

PTL 4: Japanese Patent Application Laid-Open No.H02-210459

Summary of the invention

the problem that invention will solve

For example, yet the macromolecule dispersing agent of recording in PTL 1 has poor and compatibility hydrophobic resin glue (polystyrene) conventionally, causes the inadequate dispersion of pigment.

In the use pigment derivative of recording in PTL 2 and the method for macromolecule dispersing agent, pigment disperses by the interaction of bronsted lowry acids and bases bronsted lowry.Due to this reason, in surface of pigments, form the salt with high polarity.Due to this reason, in water, to produce in the method for toner, pigment unevenly distributes in toner surface, causes the inadequate dispersion of pigment.As a result, chargedly become unstable.

The use of recording in PTL 3 wherein quinoline Azone is covalently bonded in the method for spreading agent of polymkeric substance, shows the dispersion effect of certain level in the situation that of quinoline Azone pigment.Yet not talkative the method has met nearest for the more requirement of high image quality, and the method need to further be improved.

Further, the method for recording in PTL 4 provides the inadequate dispersiveness of pigment in toner in the situation that of diketone pyrrole pigment, and can not suppress fully hazing on image.

Therefore, an object of the present invention is to provide dispersiveness and the high-strength magenta toner of magenta toner in resin glue with improvement.Another object of the present invention is to provide the magenta toner that can suppress to haze and have high transfer efficiency.

for the scheme of dealing with problems

Above object can reach by following the present invention.

That is, the invention provides a kind of toner, it comprises toner-particle, and described toner-particle contains resin glue; Have part-structure (partial structure) and have the compound at the macromolecule position of monomeric unit, described part-structure is bonded to described macromolecule position; With the magenta pigment as colorant,

Described part-structure is represented by following formula (1):

Formula (1)

[R wherein ₁, R ₂with Ar one of at least via linking group or by singly bound to described macromolecule position; Be not bonded to the R at described macromolecule position ₁and R ₂represent independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇group; The Ar that is not bonded to described macromolecule position represents aryl; Be bonded to the R at described macromolecule position ₁and R ₂represent to remove independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇the divalent group of the hydrogen atom in group; The Ar that is bonded to described macromolecule position represents to remove the divalent group of the hydrogen atom in aryl; R ₅to R ₇represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl; With

Described monomeric unit is represented by following formula (2):

Formula (2)

R wherein ₃wherein represent hydrogen atom or alkyl; And R ₄represent phenyl, carboxyl, carboxylic acid ester groups or carboxylic acyloxy amido].

the effect of invention

The present invention can provide a kind of and have high colouring power, can suppress to haze and have the cyan toner of high transfer efficiency.

With reference to accompanying drawing, further feature of the present invention becomes obvious by the description from following exemplary.

Accompanying drawing explanation

Fig. 1 be illustrate have azo skeleton structure compound (101) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 2 be illustrate have azo skeleton structure compound (110) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 3 be illustrate have azo skeleton structure compound (118) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 4 be illustrate have azo skeleton structure compound (119) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 5 be illustrate have azo skeleton structure compound (150) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 6 be illustrate have azo skeleton structure compound (108) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 7 be illustrate have azo skeleton structure compound (109) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 8 be illustrate have azo skeleton structure compound (152) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Fig. 9 be illustrate have azo skeleton structure compound (155) at 400MHz with at room temperature at CDCl ₃in ¹h NMR spectrogram.

Figure 10 be illustrate have azo skeleton structure compound (157) at 400MHz with at room temperature at CDCl ₃in ¹the figure of H NMR spectrum.

Embodiment

Below, use suitable embodiment will describe the present invention in detail.

Toner according to the present invention comprises toner-particle, and described toner-particle contains resin glue; Have part-structure and the compound with the macromolecule position of monomeric unit, described part-structure is bonded to described macromolecule position; With the magenta pigment as colorant,

Described part-structure is represented by following formula (1):

Formula (1)

[R wherein ₁, R ₂with Ar one of at least via linking group or by singly bound to described macromolecule position; Be not bonded to the R at described macromolecule position ₁and R ₂represent independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇group; The Ar that is not bonded to described macromolecule position represents aryl; Be bonded to the R at described macromolecule position ₁and R ₂represent to remove independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇the divalent group of the hydrogen atom in group; The Ar that is bonded to described macromolecule position represents to remove the divalent group of the hydrogen atom in aryl; R ₅to R ₇represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl;

Described monomeric unit is represented by following formula (2):

Formula (2)

Have compound that the part-structure being represented by above formula (1) is bonded to the macromolecule position with the monomeric unit being represented by above formula (2) have with the high-affinity of the cementing agent of water-insoluble solvent, polymerisable monomer and toner and with the high-affinity of magenta pigment.Therefore, by using this compound as pigment dispersing agent, magenta pigment is disperseed well in resin glue, provide and there is high-strength magenta toner.In addition, by adding this compound highest grade red color tone toner particles, suppressed to haze, the magenta toner with high transfer efficiency is provided.

The part-structure being represented by formula (1) is also referred to as " azo skeleton structure ".Further, the compound that has the azo skeleton structure that is bonded to the macromolecule position with the monomeric unit being represented by formula (2) is also referred to as " compound with azo skeleton structure ".Be not bonded to macromolecule position azo skeleton structure and that there is the monomeric unit being represented by formula (2) also referred to as " macromolecule position ".

First, the compound with azo skeleton structure will be described.

The compound with azo skeleton structure comprises the azo skeleton structure of having of being represented by above formula (1) and the high-affinity of magenta pigment, and have at least one monomeric unit in the monomeric unit being represented by above formula (2) and with the macromolecule position of the high-affinity of water-insoluble solvent.

First, will describe the azo skeleton structure being represented by above formula (1) in detail.

With the R in above formula (1) ₁and R ₂the example of alkyl comprise straight chain, branching or cyclic alkyl, for example methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group and cyclohexyl.

With the OR in above formula (1) ₅group and NR ₆r ₇r in group ₅to R ₇the example of alkyl comprise straight chain, branching or cyclic alkyl, for example methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group and cyclohexyl.

With the OR in above formula (1) ₅group and NR ₆r ₇r in group ₅to R ₇the example of aralkyl comprise benzyl and phenethyl.

Further, with the R in above formula (1) ₁and R ₂can optionally there is substituting group, need only the compatibility suppressing indistinctively with magenta pigment.In this case, optional substituent example comprises hydrogen atom, nitro, alkyl, amino, hydroxyl, cyano group and trifluoromethyl.

The compatibility of consideration and magenta pigment, with the R in above formula (1) ₁it can be methyl.

The compatibility of consideration and magenta pigment, with the R in above formula (1) ₂can be NR ₆r ₇group, R ₆can be hydrogen atom, and R ₇it can be phenyl.

With the Ar in above formula (1), represent aryl, and the example of this aryl comprises phenyl and naphthyl.

Further, with the Ar in above formula (1), can optionally there is substituting group, need only the compatibility suppressing indistinctively with magenta pigment.In this case, optional substituent example comprises alkyl, alkoxy, halogen atom, hydroxyl, cyano group, trifluoromethyl, carboxyl, carboxylic acid ester groups and carboxylic acyloxy amido.

Will be with the R in above formula (1) ₁, R ₂with Ar one of at least via linking group or by singly bound to macromolecule position.Be bonded to the R at macromolecule position ₁and R ₂represent to remove independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇the divalent group of the hydrogen atom in group.The Ar that is bonded to macromolecule position represents to remove the divalent group of the hydrogen atom in aryl.In this case, linking group is not particularly limited, as long as this linking group is divalent linker.From the viewpoint of easy production, this key preferably includes carboxylic acid ester bond, carboxylic acid amide key or sulfonic acid ester bond.Especially, this key more preferably comprises the secondary amide key with high synthetic yield and high bonding stability.

From the viewpoint of the compatibility with magenta pigment, the part-structure being represented by above formula (1) can be the structure being represented by following formula (3).

Formula (3)

[R wherein ₁and R ₂represent independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇group; R ₈to R ₁₂represent independently of one another hydrogen atom, COOR ₁₃group or CONR ₁₄r ₁₅group; R ₁₃to R ₁₅represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl; And R ₁, R ₂, and R ₈to R ₁₂one of at least there is the position that is connected to the macromolecule position being represented by above formula (2)].

From the viewpoint of the compatibility with magenta pigment, with the R in above formula (3) ₈to R ₁₂can be one of at least COOR ₁₃group or CONR ₁₄r ₁₅group.

With the R in above formula (3) ₁₃to R ₁₅the example of alkyl comprise methyl, ethyl, n-pro-pyl and isopropyl.

From the viewpoint of the compatibility with magenta pigment, R ₁₃can be methyl, R ₁₄can be hydrogen atom and R ₁₅can be methyl or hydrogen atom.

With the R in above formula (1) ₁, R ₂with Ar one of at least there is the connecting portion with macromolecule position.From the compatibility with magenta pigment and easy viewpoint of producing, especially, R ₂can be NR ₆r ₇group, R ₆can be hydrogen atom and R ₇it can be the phenyl having with the linking group at macromolecule position.

From the viewpoint of the compatibility with magenta pigment, the part-structure being represented by above formula (1) can be the structure being represented by following formula (4) or (5):

Formula (4)

[wherein L represents to be bonded to the divalent linker at the macromolecule position with the monomeric unit being represented by above formula (2):

Formula (5)

R wherein ₁₄and R ₁₅represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl; L represents to be bonded to the divalent linker at the macromolecule position with the monomeric unit being represented by above formula (2)].

Linking group L to the macromolecule position with in above formula (4) and (5) is not particularly limited, as long as this linking group is divalent linker.From the viewpoint of easy production, this key preferably includes carboxylic acid ester bond, carboxylic acid amide key or sulfonic acid ester bond.Especially, this key more preferably comprises the secondary amide key with high synthetic yield and high bonding stability.

In with above formula (4) and (5), equate with the compatibility of magenta pigment that derives from the difference of linking group L the position of substitution.

With the CONR in above formula (5) ₁₄r ₁₅the example of the position of substitution of group is included in situation about replacing with carboxylic acid amide in ortho position, a position or the contraposition with respect to azo group.From the viewpoint of the compatibility with magenta pigment, the replacement with carboxylic acid amide in a position or contraposition is preferred.

Next step, will describe the macromolecule position with the monomeric unit being represented by above formula (2).

To the R with in above formula (2) ₃alkyl be not particularly limited.The example of this alkyl comprises straight chain, branching or cyclic alkyl, for example methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group and cyclohexyl.

From the viewpoint of the polymerism of monomeric unit, with the R in above formula (2) ₃can be hydrogen atom or methyl.

To the R with in above formula (2) ₄carboxylic acid ester groups be not particularly limited.The example of this carboxylic acid ester groups comprises straight chain or branching ester group, for example methyl ester group, ethyl ester, n-pro-pyl ester group, isopropyl ester group, normal-butyl ester group, isobutyl ester group, sec-butyl ester group, tert-butyl group ester group, octyl group ester group, nonyl ester group, decyl ester group, undecyl ester group, dodecyl ester group, cetyl ester group, octadecyl ester group, eicosyl ester group, docosyl ester group, 2-ethylhexyl ester group, phenyl ester group and 2-hydroxyethyl ester group.

With the R in above formula (2) ₄the example of carboxylic acyloxy amido comprise straight chain or branching amide group, for example N-methyl nitrosourea base, N, N-dimethylformamide base, N-buserelin base, N, N-diethylamide base, N-isopropyl amide group, N, N-diisopropylamide base, N-normal-butyl amide group, N, N-di-n-butyl amide group, N-sec-butyl amide group, N, N-di-sec-butyl amide group, N-sec-butyl amide group, N, N-di-sec-butyl amide group, N-tert-butylamides base, N, N-di-te t-butylamide base, N-octyl group amide group, N, N-dioctyl amide group, N-nonyl amide group, N, N-dinonyl amide group, N-decyl amide group, N, N-didecyl amide group, N-undecyl amide group, N, N-bis--undecyl amide group, N-laurylamide base, N, N-bis--laurylamide base, N-cetyl amide group, N, N-bis--cetyl amide group, N-octadecyl amide group, N, N-bis--octadecyl amide group, N-eicosyl amide group, N, N-bis--eicosyl amide group, N-docosyl amide group, N, N-bis--docosyl amide group, N-phenyl amide base, N, N-diphenyl amide group, N-(2-ethylhexyl) amide group and N, N-bis-(2-ethylhexyl) amide group.

Further, with the R in above formula (2) ₄can optionally there is substituting group.Optional substituting group is not particularly limited, and only otherwise suppress to form the polymerism of the polymerisable monomer of monomeric unit, or reduces indistinctively the dissolubility of the compound with azo skeleton structure.In this case, optional substituent example comprises alkoxy for example methoxyl and ethoxy; Amino is N-methylamino and N for example, N-dimethylamino; Acyl group is acetyl group for example; With halogen atom for example fluorine atom and chlorine atom.

From the toner that contains the compound with azo skeleton structure with respect to the dispersiveness of resin glue and the viewpoint of compatibility, with the R in above formula (2) ₄can be phenyl or carboxylic acid ester groups.

The ratio of the monomeric unit that macromolecule position can be represented by above formula (2) by change is controlled the compatibility with dispersion medium.At dispersion medium, be for example cinnamic non-polar solvent in the situation that, from the viewpoint of the compatibility with dispersion medium, with the R in above formula (2) ₄the ratio can with the large monomeric unit being represented by phenyl.In the situation that dispersion medium is the solvent with polarity to a certain degree of acrylate for example, from the viewpoint of the compatibility with dispersion medium, with the R in above formula (2) ₄the ratio can with the larger monomeric unit by carboxyl, carboxylic acid ester groups or carboxylic acid amide basis representation.

As the molecular weight at macromolecule position, from the dispersed viewpoint of magenta pigment, number-average molecular weight can be more than 500.Molecular weight provides more greatly the higher dispersed effect of improving magenta pigment.Yet excessively large molecular weight is not preferred, this is because be tending towards reducing with the compatibility of water-insoluble solvent.Therefore, the number-average molecular weight at macromolecule position is preferably below 200000.In addition, consider easy production, the number-average molecular weight at macromolecule position is more preferably in 2000 to 50000 scope.

As disclosed in Japanese Patent Application Laid-Open No.2003-531001, known wherein by the method for the improvement dispersiveness of the end of branched aliphatic chain importing polyoxyalkylene carbonyl spreading agent.In addition, in the present invention, if distant pawl macromolecule position can example, the method for ATRP (atom transfer radical polymerization) is synthetic as described later, branched aliphatic chain can be imported to end.This operation can cause dispersed improvement.

The position of substitution of azo skeleton structure in the compound with azo skeleton structure can stochastic distribution, or more than one block can at one end form and unevenly distribute.

If the replacement number of the azo skeleton structure in the compound with azo skeleton structure is larger, obtain the high-affinity with magenta pigment.Yet, if this number is exceedingly large, be tending towards reducing with the compatibility of water-insoluble solvent.Therefore, this situation is not preferred.Therefore, the number of monomers 100 based on forming macromolecule position, azo skeleton structure number is preferably in 0.5 to 10 scope, and more preferably in 0.5 to 5 scope.

Shown in figure below, the azo skeleton structure being represented by above formula (1) comprises the dynamic isomer being represented by following formula (8) and (9) etc.These dynamic isomers are also included in scope of the present invention:

[the R in its Chinese style (8) and (9) ₁, R ₂with Ar separately with formula (1) in R ₁, R ₂identical with those in Ar.]。

The compound with azo skeleton structure can be synthetic according to known method.

The example that synthesizes the method for the compound with azo skeleton structure comprises that following (i) is to the method shown in (iv).

First, use the example of the following scheme illustrating, will describe method (i) in detail.

[the R in its Chinese style (11) and (12) ₁and R ₂separately with above formula (1) in R ₁and R ₂identical; Ar in formula (10) and (12) ₁represent arlydene; P ₁it is the macromolecule position by the monomeric unit acquisition of above formula (2) expression by polymerization; Q in formula (10) and (12) ₁represent and P ₁thereby reaction forms the substituting group of divalent linker L.]。

In the method for above illustrative method (i), have the compound of azo skeleton structure can be by the anil that will be represented by formula (10) and compound (11) diazo coupling the step 1 with synthetic azoic compound (12), and by condensation reaction etc., azo-compound (12) is connected to macromolecule position P ₁step 2 and synthesize.

First, step 1 will be described.In step 1, can use known method.Particularly, the example of method comprises following those that illustrate.First, by anil (10) thus in methanol solvate, under the existence of the mineral acid of for example hydrochloric acid or sulfuric acid, react synthetic corresponding diazo salt with the diazotization agent of for example sodium nitrite or nitrito-sulfuric acid.Further, diazo salt is coupled to compound (11) thus synthetic azoic compound (12).

Various anils (10) are commercially available and easily can obtain.Anil (10) also can be easily synthetic by known method.

This step can not used solvent to carry out, but for the carrying out rapidly of inhibitory reaction, preferably under the existence of solvent, carries out.Solvent is not particularly limited, and needs only not inhibitory reaction of solvent.The example of solvent comprises alcohols for example methyl alcohol, ethanol and propyl alcohol; Ester class is methyl acetate, ethyl acetate, propyl acetate for example; Ethers is diethyl ether, tetrahydrofuran He diox for example; Hydro carbons is benzene,toluene,xylene, hexane and heptane for example; Halogen-containing hydro carbons is methylene chloride, ethylene dichloride and chloroform for example; Amide-type is DMF, 1-METHYLPYRROLIDONE and N for example, N-methylimidazole alkane ketone; Nitrile is acetonitrile and propionitrile for example; Acids is formic acid, acetic acid and propionic acid for example; And water.Can be by these solvents by mixing two or more uses.Mixing ratio in the use by mixing can at random be determined according to the solubleness of solute.The use amount of solvent can determine arbitrarily, but from the viewpoint of reaction velocity, preferably in the scope of 1.0 to the 20 quality compound being represented by above formula (10) doubly.

Step 1 is carried out at the temperature in the scope of-50 ℃ to 100 ℃ conventionally, and conventionally in 24 hours, completes.

Next step, will describe the macromolecule position P synthesizing for step 2 ₁method.At macromolecule position P ₁synthetic in, can use known polymerization methods [for example, Krzysztof Matyjaszewski etc., " Chemical Reviews, " (US), American Chemical Society, 2001, Vol.101,2921-2990 page].

Particularly, the example of method comprises free radical polymerization, cationic polymerization and anionic polymerisation.From the viewpoint of easy production, can use free radical polymerization.

Free radical polymerization can be by the use of radical polymerization initiator, irradiation, Photoepolymerizationinitiater initiater and light with radioactive ray or laser etc. irradiation be used in combination or heating etc. is carried out.

Thereby radical polymerization initiator can be any radical polymerization initiator that can generate free radical initiated polymerization.Free radical polyalcohol initiating agent is selected from the compound that generates free radical by the effect of heat, light, radioactive ray and redox reaction etc.The example of this compound comprises azo-compound, organic peroxide, inorganic peroxide, organometallics and photopolymer initiating agent.In particular, the example of this compound comprises that azo is polymerization initiator for example 2,2'-azo two (isobutyronotrile), 2,2'-azo two (2-methylbutyronitrile), 2,2'-azo two (4-methoxyl-2,4-methyl pentane nitrile) and 2,2'-azo two (2,4-methyl pentane nitrile); Organic peroxide is for example benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide isopropyl carbonic ester, the tertiary own ester of benzoyl peroxide formic acid and peroxidized t-butyl perbenzoate of polymerization initiator; Inorganic peroxide is for example potassium persulfate and ammonium persulfate of polymerization initiator; With redox initiator for example hydrogen peroxide-ferrous iron be that redox initiator, benzoyl peroxide-xylidin are that redox initiator and cerium (IV) salt-ol are redox initiator.The example of Photoepolymerizationinitiater initiater comprises Benzophenone class, styrax ethers, acetophenones and thioxanthene ketone.These radical polymerization initiators can be used in combination.

The monomer that the amount of the polymerization initiator that now will use can be adjusted in based on 100 mass parts is in the scope of 0.1 to 20 mass parts, thereby obtain, has the multipolymer that target molecular weight distributes.

Above by P ₁the macromolecule position representing can produce by any method of solution polymerization, suspension polymerization, emulsion polymerization, dispersin polymerization, precipitation polymerization and bulk polymerization etc., and not restriction especially.Can dissolve for the production of the solvent of component in solution polymerization be preferred.Particularly, for example, alcohols is methyl alcohol, ethanol and 2-propyl alcohol for example, ketone is acetone and methyl ethyl ketone for example, ethers is tetrahydrofuran and Anaesthetie Ether for example, ethylene glycol monoalkyl ether class or its acetate esters, propylene-glycol monoalky lether class or its acetate esters, polar organic solvent is monoalkyl ethers of diethylene glycol class for example; With non-polar solvent for example toluene or dimethylbenzene, can use individually or use with potpourri in some cases.In these, more preferably, the solvent with the boiling point in the scope of 100 to 180 ℃ is used individually or with potpourri.

The preferred range of polymerization temperature changes according to the initiator type that will use, and not restriction especially.Particularly, polymerization is conventionally at-30 to 200 ℃, and more preferably at the temperature in the scope of 40 to 180 ℃, carries out.

By P ₁the molecular weight distribution at the macromolecule position representing and molecular structure can be used known method to control.Particularly, for example, controlling the macromolecule position of molecular weight distribution and molecular structure can use following methods to produce: the method (seeing Jap.P. No.4254292 and No.3721617) of for example using addition-breaking type chain-transferring agent, [for example use the dissociation of amine oxide free radical and the NMP method of bonding, Craig J.Hawker etc., " Chemical Reviews " (US), American Chemical Society, 2001, Vol.101, 3661-3688 page], use halogen compounds as polymerization initiator and use ATRP method that heavy metal and part carry out polymerization [for example, Masami Kamigaito etc., " Chemical Reviews " (US), American Chemical Society, 2001, Vol.101, 3689-3746 page], use dithiocarboxylic esters or xanthate compound as the RAFT method of polymerization initiator (for example, the country of international patent application No.2000-515181 is open), MADIX method (for example, WO99/05099) and DT method [for example, Atsushi Goto etc. " Journal of The American Chemical Society " (US), American Chemical Society, 2003, Vol.125, 8720-8721 page].

Next step, will describe step 2.In step 2, can use known method.Particularly, for example, by use, there is the macromolecule position P of carboxyl ₁with the azo-compound (12) with hydroxyl, can synthesize the compound that the wherein linking group with azo skeleton structure has carboxylic acid ester bond.The macromolecule position P by use in addition, with hydroxyl ₁with there is sulfonic azo-compound (12), can synthesize the compound that the wherein linking group with azo skeleton structure has sulfonic acid ester bond.The macromolecule position P further, by use with carboxyl ₁with there is amino azo-compound (12), can synthesize the compound that the wherein linking group with azo skeleton structure has carboxylic acid amide key.Particularly, the example of the method comprises and such as the method for the dehydrogenative condensation agent of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride etc. (for example using, Melvin S.Newman etc., " The Journal of Organic Chemistry, " (US), American Chemical Society, 1961, Vol.26, No.7, 2525-2528 page), and Xiao Dun-Bao Man (Schotten-Baumann) method (for example, Norman O.V.Sonntag, " Chemical Reviews, " (US), American Chemical Society, 1953, Vol.52, No.2, 237-416 page).

This step can not used solvent to carry out, but for the carrying out rapidly of inhibitory reaction, preferably under the existence of solvent, carries out.Solvent is not particularly limited, and needs only not inhibitory reaction of solvent.The example of solvent comprises ethers for example diethyl ether, tetrahydrofuran He diox; Hydro carbons is benzene,toluene,xylene, hexane and heptane for example; Halogen-containing hydro carbons is methylene chloride, ethylene dichloride and chloroform for example; Amide-type is DMF, DMA, 1-METHYLPYRROLIDONE and N for example, N-methylimidazole alkane ketone; With nitrile for example acetonitrile and propionitrile.According to the solubleness of solute, these solvents can be by mixing two or more uses.Mixing ratio in using by mixing can at random be determined.The amount of the solvent using can at random be determined.From the viewpoint of reaction velocity, this amount can be by P ₁in 1.0 to 20 quality at the macromolecule position representing scope doubly.

This step is carried out at the temperature in the scope of 0 ℃ to 250 ℃ conventionally, and conventionally in 24 hours, completes.

Next step, the example of the scheme illustrating below using, will describe method (ii) in detail:

[the R in its Chinese style (12) ₁, R ₂, Ar ₁and Q ₁separately with the scheme of method (i) in formula (12) in R ₁, R ₂, Ar ₁and Q ₁identical; Q in formula (13) ₂q in expression and formula (12) ₁thereby reaction forms the Q in formula (14) ₃substituting group; R in formula (13) and (14) ₃with the R with in above formula (2) ₃identical; Q ₃represent to form by making the Q in formula (12) ₁with the Q in formula (13) ₂the substituting group of the divalent linker that reaction forms].

In above illustrative method (ii), have azo skeleton structure compound can by the azo-compound that represented by formula (12) with by formula (13) thus represent containing vinyl compound, react the synthetic step 3 with the azo-compound (14) of polymerizable functionalities group, and the azo-compound (14) with polymerizable functionalities group is synthesized by the step 4 of the polymerisable monomer copolymerization of the monomeric unit of above formula (2) expression with formation.

First, step 3 will be described.In step 3, can use with method (i) thus in the synthetic azo-compound (14) with polymerizable functionalities group of the identical method of step 2.Particularly, for example, by using wherein Q ₂there is carboxyl substituent containing vinyl compound (13) and Q wherein ₁be the substituent azo-compound (12) with hydroxyl, can synthesize the wherein Q with polymerizable functionalities group ₃it is the substituent azo-compound (14) with carboxylic acid ester bond.By using wherein Q ₂there is hydroxyl substituent containing vinyl compound (13) and Q wherein ₁be the substituent azo-compound (12) with sulfonic acid, can synthesize the wherein Q with polymerizable functionalities group ₃it is the substituent azo-compound (14) with sulfonic acid ester bond.Further, by using wherein Q ₂there is carboxyl substituent containing vinyl compound (13) and Q wherein ₁be to there is amino substituent azo-compound (12), can synthesize wherein Q ₃it is the substituent azo-compound (14) with carboxylic acid amide key.

The various vinyl compounds (13) that contain are obtained commercially, and easily can obtain.In addition containing vinyl compound (13), can easily by known method, be synthesized.

Next step, will describe step 4.In step 4, the macromolecule position P in use and above method (i) ₁synthetic in identical method, the compound with the azo skeleton structure being represented by above formula (1) can be by synthesizing azo-compound (14) and the polymerisable monomer copolymerization forming by the monomeric unit of above formula (2) expression.

Next step, the example of the scheme illustrating below using, will describe method (iii) in detail:

[the R in its Chinese style (12) ₁, R ₂, Ar ₁and Q ₁separately with the scheme of method (i) in formula (12) in R ₁, R ₂, Ar ₁and Q ₁identical; Q in formula (15) ₄q in expression and formula (12) ₁thereby reaction forms the Q in formula (16) ₅substituting group; A represents chlorine atom, bromine atoms or iodine atom; R in formula (16) ₁, R ₂and Ar ₁represent with identical with those in above formula (12); And Q ₅represent the Q in through type (12) ₁with the Q in formula (15) ₄the linking group that reaction forms].

In above illustrative method (iii), have azo skeleton structure compound can by the azo-compound that represented by formula (12) with by formula (15) thus the halogen atom compound representing react the synthetic step 5 with the azo-compound (16) of halogen atom, and by the step 6 of the polymerisable monomer polymerization of the monomeric unit of above formula (2) expression, synthesized with formation as the azo-compound with halogen atom (16) of polymerization initiator.

First, step 5 will be described.In step 5, can use with method (i) thus in the synthetic azo-compound (16) with halogen atom of the identical method of step 2.Particularly, for example, the azo-compound (16) with halogen atom can be by being used wherein Q ₄there is carboxyl substituent containing vinyl compound (15) and Q wherein ₁there is the substituent azo-compound (12) of hydroxyl and synthesize.The azo-compound (16) with halogen atom also can be by being used wherein Q ₄to there is the substituent halogen atom compound (15) of hydroxyl and Q wherein ₁there is the substituent azo-compound (12) of sulfonic acid and synthesize.Further, having the azo-compound (16) of halogen atom can be by using wherein Q ₄to there is the substituent halogen atom compound (15) of carboxyl and Q wherein ₁to there is amino substituent azo-compound (12) and synthesize.

The example with the halogen atom compound (15) of carboxyl comprises chloroacetic acid, α-chloro-propionicacid, α-chloro-butyric acid, α-chlorine isobutyric acid, α-chloro pentane acid, α-chlorine isovaleric acid, α-chlorine caproic acid, alpha chlorophenylacetic acid, α-chlorodiphenyl acetic acid, α-chloro-α-benzenpropanoic acid, α-chloro-beta-phenylpropionic acid, bromoacetic acid, α-bromo-propionic acid, α-bromo-butyric acid, α-isobutyl bromide, α-bromine valeric acid, α-bromine isovaleric acid, α-bromocaproic acid, α-bromo-acid, α-bromine diphenyl acetic acid, α-bromo-α-benzenpropanoic acid, alpha-bromo-beta-phenyl propionic acid, iodoacetic acid, alpha-iodine propionic acid, alpha-iodine butyric acid, alpha-iodine isobutyric acid, alpha-iodine valeric acid, alpha-iodine isovaleric acid, alpha-iodine caproic acid, alpha-iodine phenylacetic acid, alpha-iodine diphenyl acetic acid, alpha-iodine-α-benzenpropanoic acid, alpha-iodine-beta-phenylpropionic acid, β-chloro-butyric acid, β-isobutyl bromide, iodine dimethyl methyl yl benzoic acid and 1-chloroethyl benzoic acid.Its acyl halide and its acid anhydrides also can be for the present invention.

The example with the halogen atom compound (15) of hydroxyl comprises 1-chlorohydrin, 1-bromoethanol, 1-iodohydrin, 1-propylene chlorohydrin, 2-bromopropyl alcohol, the chloro-2-propyl alcohol of 2-, the bromo-2-methylpropanol of 2-, 2-phenyl-1-bromoethanol and 2-phenyl-ethylene iodohydrin.

Next step, will describe step 6.In step 6, there is the polymerisable monomer that the compound of the azo skeleton structure ATRP method in can using method (i) has halogen atom azo-compound (16) by use forms monomeric unit (2) as polymerization initiator with polymerization in the presence of metallic catalyst and part and synthesize.

Metallic catalyst for ATRP method is not particularly limited.Metallic catalyst is suitably selected from least one of transition metal in periodic table 7-11 family.In low price complex and the redox catalyst (redox conjugated complex) that reversibly changes of high price complex, the example of the low price metal using particularly comprises and selects free Cu ⁺, Ni ⁰, Ni ⁺, Ni ²⁺, Pd ⁰, Pd ⁺, Pt ⁰, Pt ⁺, Pt ²⁺, Rh ⁺, Rh ²⁺, Rh ³⁺, Co ⁺, Co ²⁺, Ir ⁰, Ir ⁺, Ir ²⁺, Ir ³⁺, Fe ²⁺, Ru ²⁺, Ru ³⁺, Ru ⁴⁺, Ru ⁵⁺, Os ²⁺, Os ³⁺, Re ²⁺, Re ³⁺, Re ⁴⁺, Re ⁶⁺, Mn ²⁺and Mn ³⁺the metal of the group forming.In these, Cu ⁺, Ru ²⁺, Fe ²⁺and Ni ²⁺preferred, and Cu ⁺particularly preferred.The instantiation of monovalence copper compound comprises stannous chloride, cuprous bromide, cuprous iodide and cuprous cyanide etc., from the viewpoint of the being easy to get property of raw material, can suitably use these copper compounds.

As the part for ATRP method, conventionally, use organic ligand.Especially, the example of organic ligand comprises 2,2'-dipyridine and its derivant, 1,10-phenanthrolene and its derivant, tetramethylethylenediamine, N, N, N', N ", N " five methyl diethylentriamine, three (dimethyl aminoethyl) amine, triphenylphosphine and tributylphosphine.From the viewpoint of being easy to get property of raw material, especially, N for example, N, N', N ", " the aliphatic polyamines class such as five methyl diethylentriamine is preferred to N.

At the R with in above formula (1) ₂nR ₆r ₇group, R ₆hydrogen atom and R ₇be in the situation of phenyl, the compound with azo skeleton structure can be synthetic by following methods (iv):

[the Ar in formula (17), (19), (21) and (22) ₂represent arlydene; R in formula (18), (19), (21) and (22) ₁identical with in above formula (1); Q in formula (18) ₆represent when substituting group with formula (17) thus in the substituting group that departs from while reacting the amide group in the formula of formation (19) of amino.P ₁identical with scheme in method (i)].

In above illustrative method (iv), the compound with azo skeleton structure can synthesize by following steps: make the anil that represented by formula (17) and compound (18) thus amidation obtains the step 7 of the compound being represented by compound (19), make compound (19) with by formula (20) thus the diazonium composition coupling of the aniline analog representing obtains the step 8 of the azo-compound being represented by formula (21), use reductive agent will be by formula (21) thus the nitroreduction in the azo-compound representing be the amino step 9 obtaining by the azo-compound of formula (22) expression, with make amino in the azo-compound that formula (22) represents and by P ₁thereby the Carboxylamide in represent high and respectively synthetic molecular moiety is bonded to azo-compound the step 10 at macromolecule position.

First, step 7 will be described.In step 7, can use known method (for example, " Journal of Organic Chemistry, " 1998, Vol.63, No.4,1058-1063 page).R in compound (17) ₁be in the situation of methyl, synthesize and can replace the method for compound (16) carry out (for example, " Journal of Organic Chemistry by use diketen, " 2007, Vol.72, No.25,9761-9764 page).Various compounds (18) are that be purchased and easily available.Compound (16) also can be easily synthetic by known method.

This step can not used solvent to carry out, but for the carrying out rapidly of inhibitory reaction, preferably under the existence of solvent, carries out.Solvent is not particularly limited, and needs only not inhibitory reaction of solvent.For example, can use such as toluene and dimethylbenzene etc. and there is high boiling solvent.

Next step, will describe step 8.In step 8, azo-compound (21) can be used with identical method in step 1 in method (i) and synthesize.

Next step, will describe step 9.In step 9, for example, the reduction reaction of nitro can make to carry out with the following method.First, azo-compound (21) is dissolved in the solvent of alcohol for example, by azo-compound (21) thus in nitro under the existence of reductive agent, under normal temperature or heating condition, be reduced to amino and obtain azo-compound (22).Reductive agent is not particularly limited.The example of reductive agent comprises sodium sulphide, sodium bisulfide, sodium bisuflide, sodium polysulfide, iron, zinc, tin, SnCl ₂and SnCl ₂2H ₂o.Reduction reaction is also used the method that therein Metal Supported of for example nickel, platinum and palladium is contacted under the existence of the insoluble supported catalyst of for example activated charcoal to hydrogen to carry out.

Next step, will describe step 10.In step 10, use and identical method in step 2 in method (i), the compound with azo skeleton structure can be by by the amino in the azo-compound by formula (22) expression with by P ₁thereby the Carboxylamide in the macromolecule position representing is bonded to macromolecule position by azo-compound and synthesizes.

The compound obtaining in each step in synthetic method can be refined by separated and refining organic compound commonsense method.Example separated and process for purification comprises recrystallization or reprecipitation method with an organic solvent, and the column chromatography of use silica gel etc.By refining individually or to be used in combination these methods, can obtain highly purified compound.

Next step, will describe for according to the resin glue of toner of the present invention.

For comprising normally used Styrene-methyl Acrylic Acid Copolymer, styrene-propene acid copolymer, vibrin, epoxy resin and Styrene-Butadiene according to the example of the resin glue of toner of the present invention.Using polymerization directly to obtain in the method for toner-particle, use the monomer that forms toner-particle.Particularly, for example, can use styrene monomer for example styrene, α-methyl styrene, α-ethyl styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, adjacent ethyl styrene, an ethyl styrene and to ethyl styrene; Methyl acrylic ester monomer is methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, lauryl methacrylate, methacrylic acid stearyl, methacrylic acid Shan Yu ester, 2-Ethylhexyl Methacrylate, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, methacrylonitrile and methacrylic acid acid amides for example; Acrylic ester monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, dodecylacrylate, acrylic acid stearyl, acrylic acid Shan Yu ester, 2-ethylhexyl acrylate, acrylic acid dimethylamino ethyl ester, acrylic acid diethylamino ethyl ester, vinyl cyanide and acrylic acid amides for example; With olefin monomer for example butadiene, isoprene and cyclohexene.These monomers individually or with suitable potpourri use so that theoretical glass transition temperature (Tg) drop in the scope of 40 to 75 ℃ [see " Polymer Handbook; " (US), the third edition, J.Brandrup and E.H.Immergut edit, John Wiley & Sons, 1989, the 209-277 pages].When theoretical glass transition temperature is less than 40 ℃, be tending towards causing the storage stability of toner or the problem of durable stability aspect.Meanwhile, when theoretical glass transition temperature is greater than 75 ℃, in the situation that forming full-colour image, the transparency of toner reduces.

If used such as the non-polar resins such as styrene and for example vibrin and polycarbonate resin isopolarity resin combination, for can control example according to the resin glue of toner of the present invention as the distribution of the adjuvants such as colorant, charge control agent and wax in toner inside.For example, the in the situation that of directly using the productions such as suspension polymerization at toner-particle, polar resin is added during the polyreaction from dispersion steps to polymerization procedure.Polar resin is added according to changing the polarity of monomeric unit composition of toner-particle and the balance of the polarity of water-medium into.As a result, the concentration of resin can be controlled as to change continuously from surface to the center of toner-particle, for example, polar resin forms thin layer on the surface of toner-particle.Now, by using and the interactional polar resin of compound, colorant and charge control agent with azo skeleton structure, can control consequently colorant and with the state of expectation, exist in toner.

As can be used as according to the magenta pigment of the colorant of toner of the present invention, for example, magenta pigment can suitably be selected from the magenta pigment (for example quinoline Azone pigment, monoazo naphthols pigment, bisdiazo naphthols pigment, perylene dye, thioindigo color and diketone pyrrole pigment) of recording in " Organic Pigments Handbook " (Isao Hashimoto writes and publishes) of publishing for 2006 and use.In these, can use quinoline Azone pigment and diketone pyrrole pigment, this be because these pigment have with according to the high-affinity of pigment dispersing agent of the present invention, and can obtain the magenta toner with higher colorability.

From with according to the viewpoint of the compatibility of pigment dispersing agent of the present invention, as can be in particular according to the quinoline Azone pigment of the colorant of toner of the present invention and diketone pyrrole pigment by those of formula (6) and formula (7) expression:

Formula (6)

[R wherein ₁₆to R ₂₃represent independently of one another hydrogen atom, chlorine atom or methyl],

Formula (7)

[R ₂₄to R ₃₄represent independently of one another hydrogen atom, chlorine atom, the tert-butyl group, cyano group or phenyl].

In with above formula (6), R ₁₆to R ₂₃can at random be selected from substituting group listed above.From the viewpoint of colouring power, R ₁₆, R ₁₈to R ₂₀, R ₂₂and R ₂₃preferably hydrogen atom, and R ₁₇and R ₂₁be more preferably hydrogen atom, chlorine atom or methyl.

In with above formula (7), R ₂₄to R ₃₄can at random be selected from substituting group listed above.From the viewpoint of colouring power, R ₂₄to R ₂₅, R ₂₇to R ₃₀, and R ₃₂to R ₃₄preferably hydrogen atom, and R ₂₆and R ₃₁be more preferably hydrogen atom or phenyl.

The instantiation of the quinoline Azone pigment being represented by above formula (6) comprises C.I. paratonere 202, C.I. pigment red 122, C.I. paratonere 192 or C.I. paratonere 209.The instantiation of the diketone pyrrole pigment being represented by above formula (7) comprises C.I. paratonere 255, C.I. paratonere 254 or C.I. paratonere 264.

In the present invention, in the situation that pigment is used with the compound combination with azo skeleton structure according to the present invention, from obtaining the viewpoint with more high-strength magenta toner, especially, can suitably use magenta pigment C.I. pigment red 122, C.I. paratonere 202, C.I. paratonere 255 or C.I. paratonere 264.

Magenta pigment can be used individually or can use with its two or more potpourris.

Can be in the scope of 100:0.1 to 100:100 according to the magenta pigment in toner of the present invention and the quality ratio of components with the compound of azo skeleton structure.From the dispersed viewpoint of magenta pigment, more preferably, at 300m ²under the specific surface area of the magenta pigment below/g, quality ratio of components is in the scope of 100:0.5 to 100:20.

As according to the colorant of toner of the present invention, always use magenta pigment.Can be used in combination other colorant, as long as colorant does not suppress the dispersiveness of magenta pigment.

As the colorant of use capable of being combined, can use known magenta coloring agent.

The example of the colorant of use capable of being combined comprises that condensation azo-compound, Onion quinone, basic-dyeable fibre color lake compound, naphthol compound, benzimidazolone compound, thioindigo compound are with perylene compound.Particularly, the example comprises C.I. paratonere 2, C.I. pigment red 3, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. paratonere 23, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. paratonere 57:1, C.I. pigment red 81: 1, C.I. paratonere 144, C.I. pigment red 146, C.I. paratonere 150, C.I. paratonere 166, C.I. paratonere 169, C.I. paratonere 177, C.I. paratonere 184, C.I. paratonere 185, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 238 and C.I. paratonere 269.

The amount of these colorants that use relies on the kind of colorant, but resin glue based on 100 mass parts, and suitable total amount is 0.1 to 60 mass parts, and preferred 0.5 to 50 mass parts.

Further, in the present invention, in order to improve the physical strength of toner-particle and control to form the molecular weight of the molecule of particle, in cementing agent synthetic, also can use crosslinking chemical.

For according to the crosslinking chemical of toner of the present invention, bifunctional cross-linker's example comprises divinylbenzene, two (4-acryloxy polyethoxy phenyl) propane, glycol diacrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, 1, 5-pentanediol diacrylate, 1, 6-hexanediyl ester, neopentylglycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyglycol #200, the diacrylate of #400 and #600, propylene glycol diacrylate, polypropyleneglycol diacrylate, polyester-type diacrylate, with their dimethylacrylate.

The example of multifunctional crosslinking chemical comprises pentaerythritol triacrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, few ester acrylate and its methacrylate, 2, two (the 4-methacryloxypropyl phenyl) propane of 2-, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and trimellitic acid triallyl.

From the fixation performance of toner and resistant, damage the viewpoint of property, the monomer based on 100 mass parts, these crosslinking chemicals can be in preferred 0.05 to 10 mass parts, and more preferably in the scope of 0.1 to 5 mass parts, uses.

Further, in the present invention, in order to suppress toner for the adhering to of fixing member, wax component also can be in use in resin glue synthetic.

The example that can be used for wax component of the present invention comprises petroleum-type wax for example paraffin, microcrystalline wax, vaseline and its derivant; Montan wax and its derivant; The hydrocarbon wax being obtained by Fischer-Tropsch process and its derivant; Polyolefins wax is Tissuemat E and its derivant for example; With natural wax for example Brazil wax and candelila wax and its derivant.Derivant also comprise oxide, with segmented copolymer and the graft modification product of vinyl monomer.The example of wax component also comprises for example higher fatty alcohol of alcohols; Fatty acid is stearic acid and palmitic acid for example; Fatty acid acyl amine; Fatty acid ester; Hardened castor oil and its derivant; Vegetable wax; And animal wax.These wax components can be individually or to be used in combination.

As the amount of the wax component that will add, the total content of the cementing agent based on 100 mass parts is in preferred 2.5 to 15.0 mass parts, and more preferably in the scope of 3.0 to 10.0 mass parts.If the amount of the wax component of adding is less than 2.5 mass parts, oilless fixing is difficult.If this amount is greater than 15.0 mass parts, the amount of the wax component in toner-particle is exceedingly large.As a result, excessively a large amount of wax components exists in toner surface, and may suppress the chargeding performance of expectation.Therefore, this situation is not preferred.

When if desired, charge control agent can mix with toner according to the present invention.It is extremely best for toning system that charge control agent can be controlled friction belt electric weight.

As charge control agent, can use known charge control agent.Especially, can use the charge control agent that there is highly charged speed and can stably keep fixing carried charge.Further, in the situation that toner-particle is directly produced by polymerization, can preferably use and there is the charge control agent that oligomerization suppresses and have in water system dispersion medium substantially insoluble material.

In charge control agent, toner is controlled as electronegative those example comprises there is sulfonic group, polymkeric substance or the multipolymer of sulphonate-base or sulfonate group; Salicyclic acid derivatives and its metal complex; Monoazo metal compound; Acetylacetone metallic compound; Aromatic hydroxy-carboxylic, aromatic series list and polycarboxylic acid and its slaine, acid anhydrides, ester; Amphyl is bis-phenol for example; Urea derivative; Containing metal naphthoic acid compound; Boron compound; Quaternary ammonium salt; Calixarenes; With resene charge control agent.The example of those that are positively charged by toner comprises nigrosine and with the nigrosine modified product of fatty acid metal salts etc.; Guanidine compound; Imidazolium compounds; Quaternary ammonium salt is tributyl benzyl ammonium-1-hydroxyl-4-naphthalene sulfonate and TBuA tetrafluoroborate for example, and its analog Li is as the salt of phosphonium salt etc., and its color lake class pigment; Triphenhlmethane dye and its color lake class pigment (colouring stabilizer is wolframic acid phosphorus, molybdic acid phosphorus, tungsten acid phosphorus, tannic acid, lauric acid, gallic acid, the ferricyanide and ferrocyanide for example); The slaine of higher fatty acid; Two organic oxidation tin are Dibutyltin oxide, dioctyl tin oxide, dicyclohexyl tin oxide for example; Two organotin borates are dibutyl tin borate, dioctyl tin borate and dicyclohexyl tin borate for example; With resene charge control agent.These can be individually or be used in combination.

In toner according to the present invention, inorganic fine powder can be added into toner-particle as flowing agent.As inorganic fine powder, can use silicon dioxide, titanium dioxide, aluminium oxide or its composite oxides, and these fine powder of surface-treated.

Produce to form and comprise normally used comminuting method, suspension polymerization, suspension comminution granulation and emulsion polymerization according to the example of the toner-particle method of toner of the present invention.Carrying capacity of environment from produce and the viewpoint of particle diameter control performance, in these production methods, can be used the method that wherein toner-particle is produced in water-medium, and can use especially suspension polymerization or suspension comminution granulation.

Manufacturing according in the method for toner of the present invention, thering is the compound of azo skeleton structure and magenta pigment and be pre-mixed and prepare color compositions.Thus, can improve the dispersiveness of magenta pigment.

Color compositions can be by wet method or dry production.Consider that the compound with azo skeleton structure has the high-affinity with water-insoluble solvent, can use by can easily producing the production of color compositions of wet method of the color compositions of homogeneous.Specifically not, for example, color compositions obtains as follows.There is the compound of azo skeleton structure and ought in dispersion medium, dissolve by resin if desired.When stirring this dispersion medium, pigment powder is little by little added and mix fully with dispersion medium.Further, use for example dispersion machine of mixing roll, roller mill, bowl mill, paint mixer, dissolver, masher, sand mill and high speed mixing smelting machine, mechanical shear stress is applied to dispersion medium.Thus, magenta pigment can be imperceptibly with the stably fine grain state dispersion of homogeneous.

The dispersion medium that can be used for color compositions is not particularly limited.In order to obtain the high Pigments effect of the compound with azo skeleton structure, dispersion medium is that the situation of water-insoluble solvent is preferred.Particularly, the example of water-insoluble solvent comprises ester class for example methyl acetate, ethyl acetate and propyl acetate; Hydro carbons is hexane, octane, sherwood oil, cyclohexane, benzene, toluene and dimethylbenzene for example; With halogen-containing hydro carbons for example phenixin, triclene, tetrabromoethane.

The dispersion medium that can be used for color compositions can be polymerisable monomer.Particularly, the example of polymerisable monomer can comprise styrene, α-methyl styrene, α-ethyl styrene, o-methyl styrene, between methyl styrene, p-methylstyrene, to methoxy styrene, to styryl phenyl, to Benzene Chloride ethene, 3,4-benzene dichloride ethene, to ethyl styrene, 2,4-DMS, align butylstyrene, p-tert-butylstyrene, to positive hexyl phenenyl ethene, to n-octyl styrene, align nonyl benzene ethene, align decyl styrene, align dodecyl styrene, ethene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, bromine ethene, iodoethylene, vinyl acetate, propionate, vinyl benzoate, methacrylic acid, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, n octyl methacrylate, lauryl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid stearyl, methacrylic acid Shan Yu ester, methacrylic acid phenylester, dimethylaminoethyl methacrylate, diethyl aminoethyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic acid n-octyl, dodecylacrylate, 2-EHA, acrylic acid stearyl, acrylic acid Shan Yu ester, acrylic acid 2-chloroethene ester, phenyl acrylate, vinyl methyl ether, EVE, vinyl isobutyl base ether, ethenyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, vinyl naphthalene, vinyl cyanide, methacrylonitrile and acrylamide.

As the resin that can be used for color compositions, can use the resin can be used as according to the resin glue of toner of the present invention.Particularly, the example of resin glue comprises Styrene-methyl Acrylic Acid Copolymer, styrene-propene acid copolymer, vibrin, epoxy resin and Styrene-Butadiene.These dispersion medium can be by mixing two or more uses.Further, color compositions can be separated by the known method of for example filtration, decant or centrifuging.Solvent can be removed by washing.

Further, at production period, auxiliary agent can be added into color compositions.The instantiation of auxiliary agent for example comprises, surfactant, pigment dispersing agent, filling agent, standard agent, resin, wax, defoamer, antistatic agent, dust-proofing agent, extender, deep or light colorant, preservative agent, drying retarder, rheology control agent, wetting agent, antioxidant, UV absorbing agent, light stabilizer or its combination.These auxiliary agents can be individually or to be used in combination.The compound with azo skeleton structure can be added in advance in the production of thick pigment.

Following produce by suspension polymerization, produced according to toner-particle of the present invention.Thereby color compositions, polymerisable monomer, wax component and polymerization initiator etc. are mixed to preparation polymerizable monomer composition.Next step is particle thereby polymerizable monomer composition is scattered in water-medium by polymerizable monomer composition granulation.Then, thus the polymerization in water-medium of the polymerisable monomer in polymerizable monomer composition particle obtains toner-particle.

Thereby the polymerizable monomer composition in above step can obtain dispersion liquid by dispersible pigment composition in the first polymerisable monomer, and this dispersion liquid is mixed and prepared with the second polymerisable monomer.That is, this color compositions disperses fully in the first polymerisable monomer, and is mixed together with the second polymerisable monomer and other toner materials.Thus, magenta pigment can exist with good disperse state at toner-particle.

The example that is used for the polymerization initiator of suspension polymerization can comprise known polymerization initiator for example azo-compound class, organic peroxide class, inorganic peroxide class, organometallics class and Photoepolymerizationinitiater initiater class.In particular, the example of polymerization initiator comprises azo polymerization initiator for example 2,2'-azo two (isobutyronotrile), 2,2'-azo two (2-methylbutyronitrile), 2,2'-azo two (4-methoxyl-2,4-methyl pentane nitrile), 2,2'-azo two (2,4-methyl pentane nitrile) and dimethyl-2,2'-azo two (isobutyrate); Organic peroxide polymerization initiator class is benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide isopropyl monocarbonate, tertiary hexyl peroxide benzoate and peroxidized t-butyl perbenzoate for example; Inorganic peroxide polymerization initiator class is potassium persulfate and ammonium persulfate for example; With redox initiator class for example hydrogen peroxide-ferrous iron be that redox initiator class, BPO-xylidin are that redox initiator class and cerium (IV) salt-ol are redox initiator class.The example of Photoepolymerizationinitiater initiater comprises acetophenone class, styrax ethers and ketal class.These methods can be individually or to be used in combination.

Polymerisable monomer based on 100 mass parts, the concentration of polymerization initiator is preferably in 0.1 to 20 mass parts and more preferably in the scope of 0.1 to 10 mass parts.The kind that polymerization causes is according to polymerization slight change, but 10 hours half life temperatures of reference are used polymerization initiator individually or with potpourri.

Water-medium for suspension polymerization can contain dispersion stabilizer.As dispersion stabilizer, can use known inorganic or organic dispersion stabilizer.The example of inorganic dispersion stabilizer comprises calcium phosphate, magnesium phosphate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, calcium metasilicate, calcium sulphate, barium sulphate, bentonitic clay, silicon dioxide and aluminium oxide.The example of organic dispersion stabilizer comprises sodium salt and the starch of polyvinyl alcohol (PVA), glycerine, methylcellulose, methylhydroxypropylcellulose, ethyl cellulose, carboxymethyl cellulose.Also can use nonionic, negative ion and cationic surfactant.The example of surfactant comprises lauryl sodium sulfate, sodium tetradecyl sulfate, pentadecyl sodium sulphate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate and calcium oleate.

In dispersion stabilizer, being dissolved in sour difficult water-soluble inorganic dispersion stabilizer can use in the present invention.In the present invention, by difficult water-soluble inorganic dispersion stabilizer for the preparation of water system dispersion medium in the situation that, the viewpoint of the drop stability from polymerizable monomer composition water-medium, these dispersion stabilizers can be used in the proportional range of take with respect to polymerisable monomer as 0.2 to 2.0 mass parts of 100 mass parts.In the present invention, can to use the polymerizable monomer composition based on 100 mass parts be prepared by the water of 300 to 3000 mass parts to water-medium.

In the present invention, in the situation that preparation has wherein disperseed the water-medium of difficult water-soluble inorganic dispersion stabilizer, commercially available dispersion stabilizer can be used as it is and disperses.In order to obtain the dispersion stabilizer particle with thin homogeneous particle diameter, difficult water-soluble inorganic dispersion stabilizer can produce and prepare in water and under high-speed stirred.For example, in the situation that calcium phosphate is used as dispersion stabilizer, thereby sodium phosphate aqueous solution mixes formation calcium phosphate fine grained under high-speed stirred with calcium chloride water.Thus, can obtain preferred dispersion stabilizer.

In the situation that toner-particle according to the present invention is produced by the comminution granulation that suspends, also can obtain suitable toner-particle.Production stage in suspension comminution granulation does not have heating steps.Therefore, can suppress the resin that causes and the fusing of wax component when using low melt wax, thereby prevent the reduction of the toner glass transition temperature that causes due to fusing.Suspension comminution granulation has the selection of toner materials for wider resin glue, and does not have use vibrin as the difficulty of principal ingredient.It is favourable that vibrin is considered to conventionally on fixing performance.Due to this reason, suspension comminution granulation is not apply therein useful production method in the production of the toner that contains resin combination of suspension polymerization.

The toner-particle of being produced by suspension comminution granulation is produced as follows.First, thus color compositions, resin glue and wax component etc. are mixed and are prepared solvent compositions in solvent.Next step, thus this solvent compositions disperses in water-medium and be that particle obtains toner-particle suspending liquid by this solvent compositions granulation.Then, the suspending liquid or the decompression that solvent are obtained by heating are removed.Thus, can obtain toner-particle.

Solvent compositions in above step can disperse to prepare dispersion liquid by color compositions in the first solvent, and by dispersion liquid and the second solvent and prepare.That is, color compositions disperses fully in the first solvent, and is mixed together with the second solvent and other toner materials.Thus, magenta pigment can exist with the state better disperseing in toner-particle.

The example of solvent of comminution granulation of can be used for suspending comprises hydro carbons for example toluene, dimethylbenzene and hexane; Halogen-containing hydro carbons is methylene chloride, chloroform, ethylene dichloride, trichloroethanes and phenixin for example; Alcohols is methyl alcohol, ethanol, butanols and isopropyl alcohol for example; Polyalcohols is ethylene glycol, propylene glycol, diglycol and triethylene glycol for example; Cellosolve class is methyl cellosolve and ethyl cellosolve for example; Ketone is acetone, methyl ethyl ketone and methyl isobutyl ketone for example; Ethers is phenmethylol ethylether, phenmethylol isopropyl ether and tetrahydrofuran for example; With ester class for example methyl acetate, ethyl acetate and butyl acetate.These can use individually or with two or more potpourris.In these, thus can use and there is solvent lower boiling and that can dissolve fully resin glue and easily remove the solvent in toner-particle suspending liquid.

Resin glue based on 100 mass parts, the amount of the solvent that use is preferably in 50 to 5000 mass parts and more preferably in the scope of 120 to 1000 mass parts.

Water-medium for the comminution granulation that suspends can contain dispersion stabilizer.As dispersion stabilizer, can use known inorganic and organic dispersion stabilizer.The example of inorganic dispersion stabilizer comprises calcium phosphate, calcium carbonate, aluminium hydroxide, calcium sulphate and barium carbonate.The example of organic dispersion stabilizer comprises water-soluble polymers for example sodium salt, sodium polyacrylate and the sodium polymethacrylate of polyvinyl alcohol (PVA), methylcellulose, hydroxyethyl cellulose, ethyl cellulose, carboxymethyl cellulose; With surfactant for example neopelex, sodium stearyl sulfate, sodium oleate, sodium laurate and potassium stearate of anionic surfactant for example, cationic surfactant is lauryl amine acetic acid esters, stearylamine acetic acid esters and lauryl trimethyl ammonium chloride for example, amphoteric surfactant is lauryl dimethyl amine oxide for example, and non-ionic surfactant for example polyethylene oxide alkyl ethers, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl amine.

The viewpoint of the drop stability from solvent compositions water-medium, the resin glue based on 100 mass parts, the amount of the spreading agent that use can be in the scope of 0.01 to 20 mass parts.

In the present invention, the preferred weight average particle diameter of toner (hereinafter, being written as D4) is at 3.00 to 15.0 μ m and more preferably in the scope of 4.00 to 12.0 μ m.In the situation that D4 is in above scope, in retainer belt electrical stability, be easy to obtain high-definition image.The number average bead diameter of D4 and toner (hereinafter, be written as D1) ratio (hereinafter, being written as D4/D1) preferably below 1.35, and more preferably below 1.30, this is because keeping the high-resolution while, can suppress to haze and can improve transfer efficiency.

D4 in toner according to the present invention and D1 are regulated by the control method changing according to the method for producing toner-particle.For example, the in the situation that of suspension polymerization, concentration, reaction stirring rate or the reaction mixing time etc. of spreading agent that D4 and D1 can be used for to the preparation of water system dispersion medium by control regulate.

According to toner of the present invention, can be magenta toner or non-magenta toner.In the situation that toner according to the present invention is used as magenta toner, magnetic material can mix and use according to the toner-particle of toner of the present invention with formation.The example of such magnetic material comprises ferriferous oxide for example magnetic iron ore, maghemite and ferrite; The ferriferous oxide that contains other metal oxide; Alloy or the potpourri of for example metal of Fe, Co and Ni, or these metals and for example metal of Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W and V.The magnetic material that is suitable for especially object of the present invention is the fine grained of tri-iron tetroxide or γ-di-iron trioxide.

From the viewpoint of the developability of toner, in these magnetics, mean grain size can be 0.1 to 2 μ m (preferably 0.1 to 0.3 μ m); And as the magnetic property under 795.8kA/m, coercive force can be 1.6 to 12kA/m, magnetic saturation intensity can be 5 to 200Am ²(preferably 50 to 100Am for/kg ²/ kg), and remanent magnetization can be 2 to 20Am ²/ kg.

As the amount of these magnetic materials that will add, the resin glue based on 100 mass parts, use 10 to 200 mass parts and the preferably magnetic of 20 to 150 mass parts.

Embodiment

Hereinafter, use embodiment and comparative example, will be described herein in more detail the present invention, but the present invention will not be limited to following examples and not leave main idea of the present invention.Hereinafter, " part " and " % " is based on quality, except as otherwise noted.

Below illustrate for the synthesis of routine measuring method.

(1) measurement of molecular weight

In the present invention, the molecular weight at macromolecule position converts to calculate with tygon according to size exclusion chromatography (SEC) (SEC) with the molecular weight with the compound of azo skeleton structure.According to the measurement of the molecular weight of SEC, carry out as shown below.

The concentration that sample is added into the following eluent illustrating so that sample is 1.0%, and former state is at room temperature placed 24 hours.Thus obtained solution filters with the solvent resistance membrane filter with the aperture of 0.2 μ m.The solution of acquisition is used as sample solution, and measures under the following conditions:

Equipment: high speed GPC equipment (HLC-8220 GPC) [Tosoh Corporation manufacture],

Two of chromatographic column: LF-804 connects post,

Eluent: THF,

Flow velocity: 1.0ml/min,

Oven temperature: 40 ℃, and

Sample injection rate IR: 0.025ml.

In the calculating of the molecular weight of sample, the molecular weight calibration curve that use utilizes polystyrene standard resin [Tosoh Corporation manufactures, TSK standard styrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000 and A-500] to set up.

(2) measurement of acid number

In the present invention, the acid number at macromolecule position is measured by the following method with the acid number with the compound of azo skeleton structure.

Basic operation is carried out according to JIS K-0070.

1) accurately weigh 0.5 to 2.0g sample.By quality definition now, be M (g).

2) sample is positioned in 50ml beaker.By tetrahydrofuran/ethanol of 25ml (2/1) thus mixed liquor be added into this sample sample dissolution.

3) use the ethanolic solution of 0.1mol/l KOH, potentiometric titrimeter for titration [for example, can use Hiranuma Sangyo Co., the automatic Titration measuring equipment " COM-2500 " that Ltd. manufactures etc.] carries out.

4) amount of KOH solution is now defined as to S (ml).Meanwhile, measure blank, and the amount of the KOH that will use is defined as B (ml).

5) acid number is calculated by following formula.F is the factor of KOH solution.

(3) composition analysis

The structure at macromolecule position is used following measuring apparatus with the structure with the compound of azo skeleton structure:

¹H?NMR

JEOL, the ECA-400 that Ltd. manufactures (solvent of use: deuterochloroform), and

¹³C?NMR

FT-NMR AVANCE-600 (the solvent of use: deuterochloroform) that Bruker BioSpin Corp. manufactures

? ¹³in C NMR, by inverted gated decoupling method, use chromium acetylacetonate (III) to carry out quantitatively as relaxation reagents, and carry out composition analysis.

Embodiment 1

The compound with azo skeleton structure is obtained by following methods.

The production example > of < compound (101)

The compound (101) with azo skeleton structure is produced according to following scheme:

[wherein " co " refers to that the arrangement of the monomeric unit that shows to form multipolymer is random symbol].

First, the compound of 3.00 parts (23) is added into the chloroform of 30 parts, and with ice-cooled to below 10 ℃.Then, add the compound (24) of 2.71 parts.Then, solution is stirred 2 hours at 65 ℃.After having reacted, by chloroform extraction and concentrated for reaction product, thereby obtain the compound (25) (95.2% productive rate) of 5.43 parts.

Then, the concentrated hydrochloric acid of the water of 30.0 parts and 11.0 parts is added into the compound (26) of 5.00 parts, and by solution with ice-cooled to below 10 ℃.The sodium nitrite of 3.46 parts that is added into the water of 8.10 parts is dissolved in solution, and reaction is carried out 1 hour at the same temperature.Next step, be added into solution by the sulfaminic acid of 0.657 part, and this solution is further stirred to 20 minutes (diazonium salt solution).Then, the compound of 8.13 parts (25) is added into the water of 48.0 parts.By the solution obtaining with ice-cooled to below 10 ℃, and interpolation diazonium salt solution.Then, add the sodium carbonate dissolving of 14.3 parts in the water of 80.0 parts, and reaction is carried out 2 hours below at 10 ℃.After having reacted, add the water of 50 parts and stir 30 minutes.Then, by solid filtering, and by using the recrystallization method of DMF refining, thereby obtain the compound (27) (98.9% productive rate) of 13.2 parts.

Next step, be added into the chloroform of 30.0 parts by the triethylamine of the compound of 3.00 parts (27) and 1.20 parts, and by solution with ice-cooled to below 10 ℃.The compound of 1.03 parts (28) is added into solution, and reaction is carried out 20 minutes at the same temperature.By reaction product chloroform extraction, concentrated, and refining, thus the compound (29) (98.8% productive rate) of 3.40 parts obtained.

Next step, be added into the compound (30) of 10 parts by the DMF of 9.44 parts, the compound (29) of 1.06 parts and the azoisobutyronitrile of 0.327 part, and solution is stirred 2 hours at 80 ℃ under nitrogen atmosphere.After having reacted, reaction product is refining by the recrystallization method of use DMF, thus obtain the compound with azo skeleton structure (101) (69.0% productive rate) of 7.60 parts.

(analysis result with the compound (101) of azo skeleton structure)

[1] molecular weight measurement (GPC) result: weight-average molecular weight (Mw)=16762, number-average molecular weight (Mn)=10221

[2] measurement result of acid number: 0.0mgKOH/g

[3] ¹h NMR (400 MHz, CDCl ₃, room temperature) result (seeing Fig. 1): δ [ppm]=14.69 (s, 1H), 11.40 (s, 1H), 7.56 (s, 2H), 7.31 (s, 2H), 7.19-6.43 (m, 135H), 2.53 (s, 3H), 2.47-1.05 (m, 97H)

The production example > of < compound (110)

The compound (110) with azo skeleton structure is produced according to following scheme:

First, the compound of 3.11 parts (31) is added into the chloroform of 30 parts.By solution with ice-cooled to below 10 ℃, and add the compound (24) of 1.89 parts.Then, solution is stirred 2 hours at 65 ℃.After having reacted, by chloroform extraction and concentrated for reaction product, thereby obtain the compound (32) (96.0% productive rate) of 4.80 parts.

Next step, be added into the compound (33) of 4.25 parts by the concentrated hydrochloric acid of the methyl alcohol of 40.0 parts and 5.29 parts, and by solution with ice-cooled to below 10 ℃.The sodium nitrite dissolving of 2.10 parts is added into solution, and reaction is at room temperature carried out 1 hour in the water of 6.00 parts.Next step, further add the sulfaminic acid of 0.990 part, stirs 20 minutes (diazonium salt solution).Then, the compound of 4.51 parts (32) is added into the methyl alcohol of 70.0 parts, and by the solution obtaining with ice-cooled to below 10 ℃.Then, add diazonium salt solution.Then, add the sodium acetate dissolving of 5.83 parts in the water of 7.00 parts, and reaction is carried out 2 hours below at 10 ℃.After having reacted, add the water of 300 parts, and stir 30 minutes.Then, by solid filtering, and by using the recrystallization method of DMF refining, thereby obtain the compound (34) (96.1% productive rate) of 8.65 parts.

Next step, palladium-the activated charcoal (5% palladium) of the compound of 8.58 parts (34) and 0.4 part is added into the N of 150 parts, dinethylformamide, and by solution under hydrogen atmosphere (0.1 to 0.4MPa reaction pressure) at 40 ℃, stir 3 hours.After having reacted, by solution filter and concentrated, thereby obtain the compound (35) (87.5% productive rate) of 7.00 parts.

Next step, be added into the chloroform of 25.0 parts by the triethylamine of the compound of 5.00 parts (35) and 1.48 parts.By solution with ice-cooled to below 10 ℃, and add the compound (36) of 2.07 parts.Then, at room temperature stir 6 hours.After having reacted, by reaction product chloroform extraction, and concentrated, thus the compound (37) (97.3% productive rate) of 5.35 parts obtained.

The copper bromide (I) of next step, by the compound of 2.50 parts (37), the styrene (30) of 140 parts, the N of 1.77 parts, N, N', N ", N " five methyl diethylentriamine and 0.64 part is added into the DMF of 50.0 parts.Then, solution is stirred 45 minutes at 120 ℃ under nitrogen atmosphere.After having reacted, by reaction product chloroform extraction, and refining by using methyl alcohol to precipitate again, thus the compound with azo skeleton structure (110) (60.5% productive rate) of 86.2 parts obtained.

Use above equipment, find that the compound obtaining has the structure being represented by above formula.Analysis result illustrates as follows.

(analysis result with the compound (110) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result:

Weight-average molecular weight (Mw)=36377, number-average molecular weight (Mn)=21338

[2] acid number measurement result:

0.0mgKOH/g

[3] ¹h NMR (400MHz, CDCl ₃, room temperature) result (seeing Fig. 2): δ [ppm]=15.65 (s, 1H), 11.35 (s, 1H), 8.62 (s, 1H), 7.37-6.27 (m, 1294H), 4.06 (s, 3H), 3.98 (4.06 (s, 3H), 2.47-1.05 (m, 786H)

The production example > of < compound (118)

The compound (118) with azo skeleton structure is produced according to scheme:

First, when replacing atmosphere by nitrogen, by the propylene glycol monomethyl ether heating of 100 parts, and reflux under more than 120 ℃ solution temperatures.By the styrene of 152 parts, the butyl acrylate of 38 parts, the acrylic acid of 10 parts and peroxidized t-butyl perbenzoate [the organic peroxide polymerization initiator of 1.0 parts, NOF CORPORATION manufactures, trade name: PERBUTYL Z] potpourri through 3 hours, drop to solution.After potpourri is added dropwise to complete, agitating solution 3 hours.Then, in the temperature of solution, be increased in 170 ℃, solution is distilled under normal pressure.Solution temperature reaches after 170 ℃, solution is under reduced pressure distilled under 1hPa to 1 hour to remove desolventizing, thereby obtains resin solid product.Solid product is dissolved in tetrahydrofuran, and precipitate again with normal hexane.By the solid filtering of precipitation, thereby obtain compound (38).

Next step, be added into the tetrahydrofuran of 500 parts by the compound of 2.0 parts (35).Thereby solution is heated to 80 ℃ of dissolved compounds (35).After dissolved compound (35), temperature is reduced to 50 ℃.The compound (38) that interpolation and dissolving are 15 parts.Further, add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl) of 2.0 parts, and solution is stirred 5 hours at 50 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound with azo skeleton structure (118) of 14.8 parts.

(analysis result with the compound (118) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=21998

[2] measurement result of acid number: 7.3mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 3): δ [ppm]=199.88 (6C), 178.45,175.41 (30C), 172.96 (6C), 165.89,165.52,160.68,154.34,143.48 (143C), 134.93,134.02,132.87,131.48,127.67,125.54,123.47,120.85-120.63,118.49,116.52,63.36,52.66,52.44,40.58,29.96,26.26,18.66,13.39

The manufacture example > of < compound (119)

The compound (119) with azo skeleton structure is produced according to following scheme:

First, the compound of 3.00 parts (39) is added into the chloroform of 30 parts.By solution with ice-cooled to below 10 ℃, and add the compound (24) of 1.83 parts.Then, solution is stirred 2 hours at 65 ℃.After having reacted, by chloroform extraction and concentrated for reaction product, thereby obtain the compound (40) (97.4% productive rate) of 4.70 parts.

Next step, be added into the compound (39) of 3.77 parts by the concentrated hydrochloric acid of the methyl alcohol of 40.0 parts and 6.00 parts.By solution with ice-cooled to below 10 ℃.The sodium nitrite dissolving of 1.37 parts is added into solution, and 1 hour (diazonium salt solution) carried out in reaction at the same temperature in the water of 5.50 parts.The compound of 4.00 parts (40) is added into the methyl alcohol of 70.0 parts, and by solution with ice-cooled to below 10 ℃.Add diazonium salt solution.Then, add the sodium acetate dissolving of 8.86 parts in the water of 35.0 parts.And reaction is carried out 2 hours below at 10 ℃.After having reacted, add the water of 300 parts, stir 30 minutes.Then, by solid filtering, and by using the recrystallization method of DMF refining, thereby obtain the compound (41) (95.7% productive rate) of 7.62 parts.

Next step, palladium-the activated charcoal (5% palladium) of the compound of 7.00 parts (41) and 0.35 part is added into the N of 150 parts, dinethylformamide, and solution is stirred 3 hours at 40 ℃ under hydrogen atmosphere (0.1 to 0.4MPa reaction pressure).After having reacted, by solution filter and concentrated, thereby obtain the compound (42) (89.5% productive rate) of 5.84 parts.

Next step when replacing atmosphere by nitrogen, by the propylene glycol monomethyl ether heating of 100 parts, and refluxes under more than 120 ℃ solution temperatures.The potpourri of the peroxidized t-butyl perbenzoate [organic peroxide polymerization initiator, NOF CORPORATION manufactures, trade name: PERBUTYL Z] of the styrene of 120 parts, the acrylic acid of 10 parts and 1.0 parts was dropped to solution through 3 hours.After being added dropwise to complete of potpourri, agitating solution 3 hours.Then, when solution temperature is increased to 170 ℃, solution is distilled under normal pressure.Solution temperature reaches after 170 ℃, thereby solution is under reduced pressure distilled under 1hPa to 1 hour except desolventizing, thereby obtains resin solid product, solid product is dissolved in tetrahydrofuran, and precipitate with normal hexane again.By the solid filtering of precipitation, thereby obtain compound (43).

Next step, be added into the tetrahydrofuran of 500 parts by the compound of 1.5 parts (42).Solution is heated to 65 ℃, thus dissolved compound (42).After dissolved compound (42), temperature is reduced to 50 ℃.The compound (43) that interpolation and dissolving are 15 parts.Add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl) of 2.0 parts, and solution is stirred 5 hours at 50 ℃.Then, add the methyl alcohol of 20 parts, and solution is stirred 1 hour at 65 ℃.Then, the temperature of solution is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound with azo skeleton structure (119) of 15.8 parts.

(analysis result with the compound (119) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=13557

[2] measurement result of acid number: 0.0mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 4): δ [ppm]=200.00 (3C), 175.68 (5C), 173.84 (3C), 166.14,165.77,161.10,145.21-143.82 (113C), 138.15,137.25,135.24,131.74,127.99,127.56,125.61,123.80,118.78,116.83,116.08,111.90,59.70,52.91,52.73,46.50-37.00,26.52,18.49,14.02

The production example > of < compound (150)

The compound (150) with azo skeleton structure is produced according to following scheme:

First, the concentrated hydrochloric acid of the methyl alcohol of 25.0 parts and 6.00 parts is added into the compound (44) of 2.45 parts, and by solution with ice-cooled to below 10 ℃.The sodium nitrite dissolving of 1.37 parts is added into solution, and 1 hour (diazonium salt solution) carried out in reaction at the same temperature in the water of 5.50 parts.Then, the compound of 4.00 parts (40) is added into the methyl alcohol of 40.0 parts, and by solution with ice-cooled to below 10 ℃.Then, add diazonium salt solution.Then, add the sodium acetate dissolving of 8.86 parts in the water of 35.0 parts, and reaction is carried out 2 hours below at 10 ℃.After having reacted, add the water of 300 parts, and stir 30 minutes.Then, by solid filtering, and by using the recrystallization method of DMF refining, thereby obtain the compound (45) (95.8% productive rate) of 6.37 parts.

Next step, palladium-the activated charcoal (5% palladium) of the compound of 6.00 parts (45) and 0.3 part is added into the N of 150 parts, dinethylformamide, and solution is stirred 3 hours at 40 ℃ under hydrogen atmosphere (0.1 to 0.4MPa reaction pressure).After having reacted, by solution filter and concentrated, thereby obtain the compound (46) (87.9% productive rate) of 4.84 parts.

Next step, be added into the tetrahydrofuran of 500 parts by the compound of 1.6 parts (46).Thereby solution is heated to 65 ℃ of dissolved compounds (46).After dissolved compound (45), temperature is reduced to 50 ℃.The compound (43) that interpolation and dissolving are 15 parts.Add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl), and solution is stirred 5 hours at 50 ℃.Then, add the methyl alcohol of 20 parts, and solution is stirred 1 hour at 65 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound with azo skeleton structure (150) of 15.3 parts.

(analysis result with the compound (150) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=15374

[2] measurement result of acid number: 0.0mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 5): δ [ppm]=199.6 (4C), 176.3 (5C), 174.2 (4C), 168.8,162.7,144.0-146 (130C) .1,142.0,137.1-137.5,134.6,124.0-129.8,118.0,115.1-115.8,111.7,36.0-46.0,25.9

The production example > of < compound (107)

The compound with azo skeleton structure (107) with following structure is produced according to following scheme:

First, the concentrated hydrochloric acid of the water of 100 parts and 15.1 parts is added into the compound (47) of 10.0 parts, and by solution with ice-cooled to below 10 ℃.The sodium nitrite dissolving of 5.1 parts is added into solution, and 1 hour (diazonium salt solution) carried out in reaction at the same temperature in the water of 15.0 parts.The compound of 10.9 parts (48) is added into the methyl alcohol of 150.0 parts, and by solution with ice-cooled to below 10 ℃.Then, add diazonium salt solution.Then, add the sodium acetate dissolving of 7.1 parts in the water of 50.0 parts, and reaction is carried out 2 hours below at 10 ℃.After having reacted, thereby the solid filtering of precipitation is obtained to solid.By aqueous dispersion and washing and filtration for solid, thereby obtain the dye composition (49) (70.8% productive rate) of 15.6 parts.

Next step, the compound of 4.2 parts (49) is added into the pyridine of 50 parts, and dissolves.With under ice-cooled, add and dissolve the compound (50) of 2.6 parts.By solution with ice-cooled lower stirring 10 hours.After having reacted, by reaction product chloroform extraction.2M hydrochloric acid washed twice by reaction product with 100 parts, and with the water washing twice of 150 parts, and concentrated, thus thick refining product obtained.By slightly refining product chloroform extraction, and by precipitating again refining with heptane.Thus, obtain the compound (51) (71.5% productive rate) of 4.5 parts.

Next step when replacing atmosphere by nitrogen, by the propylene glycol monomethyl ether heating of 100 parts, and refluxes under more than 120 ℃ solution temperatures.By the styrene of 61.7 parts, N-(2-hydroxyethyl) acrylamide of 3.6 parts and peroxidized t-butyl perbenzoate [the organic peroxide polymerization initiator of 1.0 parts, NOF CORPORATION manufactures, trade name: PERBUTYL Z] potpourri through 3 hours, drop to solution.After being added dropwise to complete of potpourri, agitating solution 3 hours.Then, at solution temperature, be increased in 170 ℃, solution is distilled under normal pressure.Solution temperature reaches after 170 ℃, solution is under reduced pressure distilled under 1hPa to 1 hour to remove desolventizing, thereby obtains resin solid product.Solid product is dissolved with tetrahydrofuran, and precipitate again with normal hexane.Thereby the solid filtering of precipitation is obtained to compound (52).

Next step, the compound of 63.0 parts (52) dissolves in the DMF of 100 parts.With under ice-cooled, add the sodium hydride of 0.2 part, and agitating solution 1 hour.Then, add and dissolve the compound (51) of 1.0 parts.Under nitrogen atmosphere, solution is stirred 27 hours under the solution temperature of 90 ℃.Then, reaction solution precipitated with methyl alcohol again and refine, thereby obtaining the compound (53) of 8.1 parts.

Next step dissolves the compound of 6.6 parts (53) in the tetrahydrofuran of 400 parts.Thereby the 6M sodium hydrate aqueous solution of 5.1 parts is added to dissolved compound (53).Then, solution is at room temperature stirred 12 hours.The pH of reaction solution is adjusted to below 1 with concentrated hydrochloric acid.Then, thus solution distillation is obtained to residue.By residue chloroform extraction, and refining by precipitating again with methyl alcohol, thus obtain the compound with azo skeleton structure (107) of 5.0 parts.

(analysis result with the compound (107) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=13835

[2] ¹³c NMR (600MHz, CDCl ₃, room temperature) result:

δ[ppm]＝178.00(5C)、173.00(3C)、167.76、165.97、144.93、-139.91(118C)、135.00-123.00、115.56、72.13、68.80、61.79、47.00-33.00

The production example > of < compound (108)

The compound (108) with azo skeleton structure is produced according to following scheme:

First, the concentrated hydrochloric acid of the methyl alcohol of 40.0 parts and 9.72 parts is added into the compound (54) of 4.00 parts, and by solution with ice-cooled to below 10 ℃.The sodium nitrite dissolving of 2.21 parts is added into solution, and 1 hour (diazonium salt solution) carried out in reaction at the same temperature in the water of 9.00 parts.Then, the compound of 4.67 parts (48) is added into the methyl alcohol of 50.0 parts, and by solution with ice-cooled to below 10 ℃.Then, add diazonium salt solution.Then, add the sodium acetate dissolving of 14.4 parts in the water of 60.0 parts, and reaction is carried out 2 hours below at 10 ℃.After having reacted, add the water of 300 parts, stir 30 minutes.Then, by solid filtering, and by using the recrystallization method of DMF refining, thereby obtain the compound (55) (94.1% productive rate) of 8.46 parts.

The compound of 8.00 parts (55) is added into the tetrahydrofuran of 80.0 parts.Thereby solution is heated to 65 ℃ of dissolved compounds (55).After dissolved compound (55), temperature is reduced to 50 ℃.The compound (39) that interpolation and dissolving are 3.58 parts.Add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl) of 7.46 parts, and solution is stirred 5 hours at 50 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound (56) (90.1% productive rate) of 10.0 parts.

Next step, palladium-the activated charcoal (5% palladium) of the compound of 9.50 parts (56) and 0.45 part is added into the N of 150 parts, dinethylformamide, and solution is stirred 3 hours at 40 ℃ under hydrogen atmosphere (0.1 to 0.4MPa reaction pressure).After having reacted, by solution filter and concentrated, thereby obtain the compound (57) (87.5% productive rate) of 7.73 parts.

The compound of 7.6 parts (57) is added into the tetrahydrofuran of 1500 parts.Thereby solution is heated to 65 ℃ of dissolved compounds (57).After dissolved compound (57), temperature is reduced to 50 ℃.The compound (43) that interpolation and dissolving are 60.5 parts.Add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl) of 24.2 parts, and solution is stirred 5 hours at 50 ℃.Then, add two (2-ethylhexyl) amine of 300 parts, and solution is stirred 1 hour at 65 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound with azo skeleton structure (58) of 63.1 parts.

Next step, the compound of 63.0 parts (58) dissolves in the tetrahydrofuran of 3000 parts.Add the 6M sodium hydrate aqueous solution of 300 parts, thus dissolved compound (58).Solution is at room temperature stirred 12 hours.The pH of reaction solution is adjusted to below 1 with concentrated hydrochloric acid.Then, thus solvent distillation is obtained to residue.By residue chloroform extraction, and refining by precipitating again with methyl alcohol, thus obtain the compound with azo skeleton structure (108) of 54.1 parts.

(analysis result with the compound (108) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=15205

[2] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 6):

δ[ppm]＝175.99(6C)、174.46(3C)、170.00、167.00-163.00、152.00-140.00(120C)、137.80、135.00-123.00、120.00-113.00、53.00-32.00)、31.00-28.00、28.00-26.00、24.00-22.00、13.84、11.00-9.00

The production example > of < compound (109)

First, the concentrated hydrochloric acid of the methyl alcohol of 50.0 parts and 12.2 parts is added into the compound (54) of 5.00 parts, and by solution with ice-cooled to below 10 ℃.The sodium nitrite dissolving of 2.77 parts is added into solution, and 1 hour (diazonium salt solution) carried out in reaction at the same temperature in the water of 11.0 parts.Then, the compound of 3.72 parts (59) is added into the methyl alcohol of 40.0 parts, and by solution with ice-cooled to below 10 ℃.Then, add diazonium salt solution.Then, add the sodium acetate dissolving of 17.9 parts in the water of 70.0 parts, and reaction is carried out 2 hours below at 10 ℃.After having reacted, add the water of 300 parts, stir 30 minutes.Then, by solid filtering, and by using the recrystallization method of DMF refining, thereby obtain the compound (60) (81.4% productive rate) of 7.43 parts.

By the compound (61) of the compound of 1.9 parts (60) and 10.0 parts thus be added into the DMA dissolved compound of 100 parts.Add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl) of 3.0 parts, and solution is at room temperature stirred 12 days.Reaction solution is precipitated and refined with the methyl alcohol of 1000 parts.Thus, obtain the compound with azo skeleton structure (109) of 9.2 parts.

(analysis result with the compound (109) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=23171

[2] measurement result of acid number: 0.0mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 7): δ [ppm]=167.08 (9C), 165.76,164.37,150.00-143.00 (245C), 141.14,135.37,135.00-122.00,122.00-117.00,114.93,51.00-38.00

The production example > of < compound (152)

The compound (152) with azo skeleton structure is produced according to following scheme:

The concentrated hydrochloric acid of the DMF of 100.0 parts and 21.4 parts is added into the compound (62) of 10.0 parts, and by solution with ice-cooled to below 5 ℃.The sodium nitrite dissolving of 5.28 parts is added into solution, and reaction is carried out 30 minutes at the same temperature in the water of 20.0 parts.Next step, add the sulfaminic acid of 1.00 parts, and further stir 30 minutes (diazonium salt solution).The sal tartari of the compound of 15.5 parts (40) and 47.6 parts is added into the DMF of 150.0 parts, and by solution with ice-cooled to below 5 ℃.Add diazonium salt solution, and reaction is carried out 2 hours at the same temperature.After having reacted, reaction solution is expelled in the water of 50 parts, then, thereby add concentrated hydrochloric acid, regulates pH to 1, and stir 30 minutes.By the solid filtering of precipitation, and with the water washing of 150 parts.Then, solid is disperseed and washing with the methyl alcohol of 150 parts, thereby obtain the compound (63) (88.3% productive rate) of 22.4 parts.

Next step, be added into the DMF of 300 parts by the compound of 20.0 parts (63), thereby and solution is heated to 70 ℃ of dissolved compounds (63).Solution is cooled to room temperature.Add the palladium-activated charcoal (5% palladium) of 2.28 parts, and by solution under hydrogen atmosphere (0.1 to 0.4MPa reaction pressure) stirring at room 6 hours.After having reacted, filtering solution, and solvent is under reduced pressure distilled.Then, reaction product is disperseed and washing with methyl alcohol, thereby obtain the compound (64) (94.6% productive rate) of 16.3 parts.

Next step, be added into the toluene of 250 parts by the compound of 25.0 parts (43), and dissolve.Reaction solution is cooled to below 5 ℃.Little by little drip the ethanedioly chloride of 11.6 parts.When solution temperature is little by little reduced to room temperature, agitating solution 15 hours.After solvent is under reduced pressure distilled, reaction product is dissolved in the DMA of 163 parts again.Add the compound (64) of 3.00 parts, solution is stirred 3 hours at 65 ℃.The methyl alcohol of 27.8 parts is added into reaction solution, and reaction solution is stirred to other 3 hours at 65 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, reaction solution is expelled in methanol/water.The sediment of precipitation is filtered, and by refining by methanol wash, thereby the compound with azo skeleton structure (152) of 26.6 parts obtained.

(analysis result with the compound (152) of azo skeleton structure)

[1] result of GPC: number-average molecular weight (Mn)=9,757

[2] measurement result of acid number: 4.1mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 8): δ [ppm]=199.5 (3C), 179.4 (1C), 176.2 (2C), 174.3-173.6 (3C), 170.1,170.5,168.6 (3C), 162.5 (3C), 146.0-144.0 (97C), 138.2,137.3,129.5,128.2-127.1,125.6-125.3,116.3,115.5,112.1,50.9,46.3,45.9,44.1-43.8,42.5,41.0,40.3,38.0,35.2,26.2,21.5,21.3,16.6,11.9

The production example > of < compound (155)

The compound (155) with azo skeleton unit is produced according to following scheme:

First, when replacing atmosphere by nitrogen, by the propylene glycol monomethyl ether heating of 100 parts, and reflux under more than 120 ℃ solution temperatures.By the styrene of 6.0 parts, the butyl acrylate of 3.0 parts, the acrylic acid of 1.0 parts and peroxidized t-butyl perbenzoate [the organic peroxide polymerization initiator of 1.0 parts, NOF CORPORATION manufactures, trade name: PERBUTYL Z] potpourri through 3 hours, drop to solution.After being added dropwise to complete of potpourri, agitating solution 3 hours.Then, at solution temperature, be increased in 170 ℃, solution is distilled under normal pressure.Solution temperature reaches after 170 ℃, solution is under reduced pressure distilled under 1hPa to 1 hour to remove desolventizing, thereby obtains resin solid product.Solid product is dissolved in tetrahydrofuran, and precipitate again with normal hexane.By the solid filtering of precipitation, thereby obtain compound (65).

Next step, be added into the tetrahydrofuran of 500 parts by the compound of 2.0 parts (46).Thereby solution is heated to 80 ℃ of dissolved compounds (46).After compound (46) dissolves, temperature is reduced to 50 ℃.The compound (65) that interpolation and dissolving are 15 parts.Add 1-ethyl-3-(3-methylamino propyl group) carbodiimide hydrochloride (EDCHCl) of 2.0 parts, and solution is stirred 5 hours at 50 ℃.Then, add the docosanol of 2.0 parts, and solution is stirred 1 hour at 65 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound with azo skeleton structure (155) of 12.8 parts.

(analysis result with the compound (155) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=16293

[2] measurement result of acid number: 4.2mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Fig. 9): δ [ppm]=199.52 (3C), 175.81 (36C), 173.62 (3C), 168.95,162.77,145.21,143.82 (64C), 138.73,137.80,135.12,128.22,126.18,118.55,116.21,112.02,63.9,46.50-37.00,32.86,32.02,30.60,29.80,29.48,25.92,22.80,19.19,14.28,13.83

The production example > of < compound (157)

The compound (157) with azo skeleton unit is produced according to following scheme:

First, when replacing atmosphere by nitrogen, by the propylene glycol monomethyl ether heating of 100 parts, and reflux under more than 120 ℃ solution temperatures.By the styrene of 11.5 parts, the acrylic acid stearyl of 1.0 parts, the acrylic acid of 0.5 part and peroxidized t-butyl perbenzoate [the organic peroxide polymerization initiator of 1.0 parts, NOF CORPORATION manufactures, trade name: PERBUTYL Z] potpourri through 3 hours, drop to solution.After being added dropwise to complete of potpourri, agitating solution 3 hours.Then, at solution temperature, be increased in 170 ℃, solution is distilled under normal pressure.Solution temperature reaches after 170 ℃, solution is under reduced pressure distilled under 1hPa to 1 hour to remove desolventizing, thereby obtains resin solid product.Solid product is dissolved in tetrahydrofuran, and precipitate again with normal hexane.Thereby the solid filtering of precipitation is obtained to compound (66).

Next step, be added into the tetrahydrofuran of 500 parts by the compound of 2.0 parts (46).Thereby solution is heated to 80 ℃ of dissolved compounds (46).After compound (46) dissolves, temperature is reduced to 50 ℃.The compound (66) that interpolation and dissolving are 15 parts.Add 1-ethyl-3-(3-methylamino propyl group) carbodiimide hydrochloride (EDCHCl) of 2.0 parts, and solution is stirred 5 hours at 50 ℃.Then, solution temperature is little by little reduced to room temperature, and solution is stirred and spent the night.Thus, complete reaction.After having reacted, by solution filter, concentrated and by precipitating again refining with methyl alcohol.Thus, obtain the compound with azo skeleton structure (157) of 12.5 parts.

(analysis result with the compound (157) of azo skeleton structure)

[1] measurement of molecular weight (GPC) result: number-average molecular weight (Mn)=22047

[2] measurement result of acid number: 0.0mgKOH/g

[3] ¹³c NMR (600MHz, CDCl ₃, room temperature) result (seeing Figure 10): δ [ppm]=199.64 (3C), 176.08 (8C), 173.85 (3C), 170.70,168.84,162.77,145.51 (93C), 144.18,138.50,135.25,128.26,127.89,125.93,118.67,116.68,112.48,64.26,50-36.00,32.18,29.57,26.38,22.66,14.46

Carry out operation identical in the production example with the compound with azo skeleton structure (101), (107) to (110), (118), (119), (150), (152), (155) and (157), thereby produce compound (102) to (106), (111) to (117), (120) to (149), (151), (153), (154), (156), (158) and (159) with azo skeleton structure.

The compound with azo skeleton structure according to the present invention is shown in following table 1-1 and table 1-2.

Table 1-1 is according to the compound with azo skeleton unit of the present invention

Table 1-2 has the compound of azo skeleton unit according to the present invention

Table 1-2 (Continued)

[in table 1-1 and table 1-2, α represents to be positioned at the end group in structure left side; " Pr (i) " represents not replace isopropyl; " Ph " represents unsubstituted phenyl; " Et " represents ethyl; " tBu " represents the tert-butyl group.]

[be illustrated in below the X in table 1 ₁, X ₂, Y ₁to Y ₈, Z ₁, W, R ₁-1 to R ₁-3, R ₂-1 to R ₂-7 and R ₁₀-1 to R ₁₀-6 structure.]

[in formula (W), R ₁, R ₂, and R ₈to R ₁₂represent separately the substituting group shown in table 1; At X ₁, X ₂, Y ₁to Y ₈, Z ₁, R ₁-1 to R ₁-3, R ₂-1 to R ₂-4 and R ₁₀-1 to R ₁₀" * " in-6 represents the connecting portion with main polymer chain; At R ₁-1 to R ₁-3, R ₂-1 to R ₂-4 and R ₁₀-1 to R ₁₀"+" in-6 represents the connecting portion with the structure being represented by formula (W).]

Embodiment 2

First, according in the toner production run of suspension polymerization, the dispersible pigment dispersion that contains magenta pigment and the compound with azo skeleton structure are prepared by following methods.

The preparation example 1> of < dispersible pigment dispersion

Mix the compound, the compound with azo skeleton structure (150) of 1.8 parts, the styrene as water-insoluble solvent of 180 parts and the beaded glass (diameter of 1mm) of 130 parts that by following general formula (160), are represented as colorant of 18.0 parts.Use Attritor[NIPPON COKE & ENGINEERING CO., LTD. manufactures], dispersed mixture 3 hours.By potpourri screen filtration, thereby obtain dispersible pigment dispersion (DIS 1).

Compound (160)

The preparation example 2> of < dispersible pigment dispersion

Except using the compound (101) to (149) and the compound with azo skeleton structure (150) in (151) to (159) replacement dispersible pigment dispersion preparation example 1 with azo skeleton structure, carry out identical operation.Thus, obtain dispersible pigment dispersion (DIS 2) to (DIS 59).

The preparation example 3> of < dispersible pigment dispersion

Except using the compound being represented by following general formula (161) to (163) to replace respectively the compound being represented by formula (160) as colorant in dispersible pigment dispersion preparation example 1, carrying out identical operation.Thus, obtain dispersible pigment dispersion (DIS 60) to (DIS 62).

Compound (161)

Compound (162)

Compound (163)

The preparation example 4> of < dispersible pigment dispersion

Compound (107), (110), (119), (152) and (157) except using with azo skeleton structure replace, the compound with azo skeleton structure (150) in dispersible pigment dispersion preparation example 3, carrying out identical operation.Thus, obtain dispersible pigment dispersion (DIS 63) to (DIS 77).

Comparative example 1

Using the dispersible pigment dispersion that shows evaluation index as benchmark with relatively prepared by following methods with dispersible pigment dispersion.

For comparative compound 1 of the present invention, be the trade name DISPARLON DA-703-50[Kusumoto Chemicals that PTL 1 records, Ltd. manufactures, the acid number of 15mgKOH/g, the amine value of 40mgKOH/g].

The preparation example 1> of dispersible pigment dispersion for < benchmark

In the preparation example 1 of the dispersible pigment dispersion in embodiment 2, do not add the compound (150) with azo skeleton structure, carry out identical operation.Thus, obtain dispersible pigment dispersion (DIS 78) for benchmark.

The preparation example 2> of dispersible pigment dispersion for < benchmark

In the preparation example 3 of the dispersible pigment dispersion in embodiment 2, do not add the compound (150) with azo skeleton structure, carry out identical operation.Thus, obtain for benchmark dispersible pigment dispersion (DIS 79) to (DIS 81).

< relatively uses the preparation example 1> of dispersible pigment dispersion

Except adding the comparative compound 1 of 1.8 parts, replace, the compound with azo skeleton structure (150) in the preparation example 1 of the dispersible pigment dispersion in embodiment 2, carrying out identical operation.Thus, obtain and relatively use dispersible pigment dispersion (DIS 82).

< relatively uses the preparation example 2> of dispersible pigment dispersion

Except adding the comparative compound 1 of 1.8 parts, replace, the compound with azo skeleton structure (150) in the preparation example 3 of the dispersible pigment dispersion in embodiment 2, carrying out identical operation.Thus, obtain and relatively use dispersible pigment dispersion (DIS 83) to (DIS 85).

Embodiment 3

Dispersible pigment dispersion is evaluated by following methods.

According to the dispersiveness of the pigment of the compound with azo dyes skeleton structure of the present invention, by the measurement of luster of filming that carries out being formed by dispersible pigment dispersion, evaluate.That is, dispersible pigment dispersion is taken out by transfer pipet, and with line style form, place on the top of superfine art paper [Ltd. manufactures for SA Kanefuji 180kg 80 * 160, Oji Paper Co.].Use coiling rod (#10), dispersible pigment dispersion is applied to art paper equably.After dry coating, gloss (reflection angle: 75 °) is used to glossmeter Gloss Meter VG2000[Nippon Denshoku Industries Co., Ltd. manufactures] measure, and according to following standard evaluation.Along with magenta pigment is more carefully disperseed, the flatness of filming further improves and gloss further improves.

The evaluation criterion of dispersible pigment dispersion hereinafter, is shown.

A: the improvement rate of gloss number is more than 30%.

B: the improvement rate of gloss number is to be not less than 20% and be less than 30%

C: the improvement rate of gloss number is to be not less than 10% and be less than 20%

D: the improvement rate of gloss number is to be less than 10%

The gloss number of the dry coating of the improvement rate of the gloss number of dispersible pigment dispersion (DIS1)-(DIS59) and dry coating (DIS82) based on dispersible pigment dispersion (DIS78).

The gloss number of the dry coating of the improvement rate of the gloss number of dispersible pigment dispersion (DIS60), (DIS63), (DIS66), (DIS69), (DIS72), (DIS75) and dry coating (DIS83) based on dispersible pigment dispersion (DIS79).

The gloss number of the dry coating of the improvement rate of the gloss number of dispersible pigment dispersion (DIS61), (DIS64), (DIS67), (DIS70), (DIS73), (DIS76) and dry coating (DIS84) based on dispersible pigment dispersion (DIS80).

The gloss number of the dry coating of the improvement rate of the gloss number of dispersible pigment dispersion (DIS62), (DIS65), (DIS68), (DIS710), (DIS74), (DIS77) and dry coating (DIS85) based on dispersible pigment dispersion (DIS81).

In this is evaluated, when the improvement rate of gloss number is 10% when above, judgement pigment-dispersing is good.

The evaluation result of the pigment-dispersing in the present invention is being shown 2-1 to showing shown in 2-2.

The evaluation result of table 2-1 pigment-dispersing

The evaluation result of table 2-2 pigment-dispersing

Embodiment 4

Next step, toner according to the present invention is produced according to following methods by suspension polymerization.

< toner is produced routine 1>

By the 0.1mol/l-Na of the ion exchange water of 710 parts and 450 parts ₃pO ₄aqueous solution is added into the four neck flasks that comprise high-speed mixing equipment T.K. mixer [PRIMIX Corporation manufacture] of 2L.Revolution is adjusted to 12000rpm.Temperature is increased to 60 ℃.By the 1.0mol/l-CaCl of 68 parts ₂thereby aqueous solution is little by little added wherein preparation and is contained thin, difficult water miscible dispersion stabilizer Ca ₃(PO ₄) ₂water-medium.Next step, be heated to 60 ℃ by following composition, and under 5000rpm, use high-speed mixing equipment T.K. mixer [PRIMIX Corporation manufacture] dissolve equably or disperse.

132 parts of dispersible pigment dispersions (DIS 1)

46 parts of styrene monomers

34 parts of n-butyl acrylate monomers

10 parts of polar resins [saturated polyester resin (bisphenol-A of terephthalic acid (TPA)-propylene oxide modification, 15 acid number, 6000 peak molecular weight)]

Ester type waxes (maximum endothermic peak=70 ℃ in dsc measurement, Mn=704) 25 parts

2 parts of salumin compounds [ORIENT CHEMICAL INDUSTRIES CO., LTD. manufactures, trade name: BONTRON E-108]

0.1 part of divinyl benzene monomer

Using 10 parts as 2 of polymerization initiator, 2'-azo two (2,4-methyl pentane nitrile) is added into composition.The potpourri of acquisition is added into water-medium.When revolution remains on 12000rpm, granulation is carried out 15 minutes.Then, stirring machine is changed into propeller agitation blade from high-speed mixing equipment.Be aggregated under the solution temperature of 60 ℃ and continue 5 hours.Then, solution temperature is increased to 80 ℃, and polymerization continues 8 hours.After polyreaction completes, by the under reduced pressure distillation at 80 ℃ of remaining monomer.Then, by being cooled to 30 ℃, obtain polymer fine particles dispersion liquid.

The polymer fine particles dispersion liquid of acquisition is placed into washing container.When stirring polymer fine particles dispersion liquid, add the hydrochloric acid of distillation.Further, thus being stirred in to carry out dissolving for 2 hours under 1.5 pH contains Ca ₃(PO ₄) ₂phosphoric acid and the compound of calcium.Thereby use filtrator to carry out Separation of Solid and Liquid solution and obtain polymer fine particles.Polymer fine particles is placed in water, thereby and stirs and again prepare dispersion liquid.Then, dispersion liquid is used filtrator carry out Separation of Solid and Liquid.Repeated polymerization fine grained in water disperse again and the Separation of Solid and Liquid of dispersion liquid until remove fully and contain Ca ₃(PO ₄) ₂phosphoric acid and the compound of calcium.Then, the polymer fine particles that finally carries out Separation of Solid and Liquid is dry fully with dryer, thus obtain toner-particle.

Use Henschel mixer [NIPPON COKE & ENGINEERING CO., LTD. manufactures] to be dry mixed and to close 5 minutes the toner-particle with hexamethyldisilazane (number average bead diameter of the primary particle of 7nm) surface-treated hydrophobic silica fine powder, the rutile titanium dioxide fine powder (the primary particle number average bead diameter of 45nm) of 0.15 part, the rutile titanium dioxide fine powder (the primary particle number average bead diameter of 200nm) of the 0.5 part acquisition based on 100 parts of 1.0 parts.Thus, obtain toner (TNR 1).

< toner is produced routine 2>

Except using dispersible pigment dispersion (DIS 2) to (DIS 77) to replace the dispersible pigment dispersion (DIS 1) in toner production example 1, according to toner of the present invention (TNR 2) to (TNR 77) to obtain with mode identical in toner production example 1.

Comparative example 2

The benchmark that shows evaluation index is with relatively being produced by following methods with toner according to toner of the present invention of producing in toner and embodiment 4.

The production example 1> of toner for < benchmark

Except using the dispersible pigment dispersion (DIS 1) in dispersible pigment dispersion (DIS 78) to (DIS 81) replacement toner production example 1, toner for benchmark (TNR 78) to (TNR 81) is to obtain with mode identical in toner production example 1.

< relatively produces routine 1> with toner

Except using the dispersible pigment dispersion (DIS 1) in dispersible pigment dispersion (DIS 82) to (DIS 85) replacement toner production example 1, relatively use toner (TNR 82) to (TNR 85) to obtain with mode identical in toner production example 1.

Embodiment 5

Next step, toner according to the present invention is produced according to following methods by suspension comminution granulation.

< toner is produced routine 3>

Mix the ethyl acetate of 180 parts, compound, the compound with azo skeleton structure (150) of 1.8 parts and the beaded glass (φ is 1mm) of 130 parts of formula (160) of 18 parts.Use Attritor[NIPPON COKE & ENGINEERING CO., LTD. manufactures], potpourri is disperseed 3 hours, and with screen filtration, thereby prepare dispersible pigment dispersion.

Thereby use bowl mill to disperse to obtain for 24 hours the method for producing toner and toner mixed liquor of 200 parts following composition.

96.0 parts of dispersible pigment dispersions

85.0 parts of polar resins [saturated polyester resin (bisphenol-A of propylene oxide modification and the condensed polymer of phthalic acid, Tg=75.9 ℃, Mw=11000, Mn=4200,11 acid number)]

Chloroflo (fischer-tropsch wax, maximum endothermic peak=80 ℃ in dsc measurement, Mw=750) 9.0 parts

2 parts of salumin compounds [LTD. manufactures for BONTRON E-108, ORIENT CHEMICAL INDUSTRIES CO.]

10.0 parts, ethyl acetate (solvent)

Thereby use bowl mill disperse to dissolve for 24 hours carboxymethyl cellulose and obtain water-medium following composition.

20.0 parts, calcium carbonate (applying with acrylic copolymer)

0.5 part of carboxymethyl cellulose [Ltd. manufactures for Celogen BS-H, Dai-ichi Kogyo Seiyaku Co.]

99.5 parts of ion exchange waters

The water-medium of 1200 parts is placed into high-speed mixing equipment T.K. homo-mixer [PRIMIX Corporation manufacture].When water-medium being used rotating vane stir, add the method for producing toner and toner mixed liquor of 1000 parts under the peripheral speed of 20 m/sec.In temperature, when 25 ℃ of maintenances are constant, water-medium is stirred 1 minute, thereby obtain suspending liquid.

The suspending liquid of 2200 parts is being used to FULLZONE Impeller[Kobelco Eco-Solutions Co., Ltd. manufactures] under the peripheral speed of 45 m/min, stir in, solution temperature keeps constant at 40 ℃.Use fan blower, thus by the gas phase on suspending liquid forcibly sucking-off start removing of solvent.Now, from starting 15 minutes except desolventizing, add 1% the ammoniacal liquor of being diluted to as 75 parts of ionic substance.Then,, from starting 1 hour except desolventizing, add the ammoniacal liquor of 25 parts.Then,, from starting 2 hours except desolventizing, add the ammoniacal liquor of 25 parts.Finally, from starting 3 hours except desolventizing, add the ammoniacal liquor of 25 parts.The ammoniacal liquor total amount that will add is 150 parts.Further, at solution temperature, remain in 40 ℃, thereby temperature is removed to desolventizing (ethyl acetate) from suspended particle in 17 hours from starting to keep except desolventizing.Thus, obtain toner dispersion liquid.

By the 10mol/l hydrochloric acid of 80 parts be added into 300 parts at solvent, remove the toning dispersion liquid obtaining in step.Further, by 0.1mol/l sodium hydrate aqueous solution neutralization for toner dispersion liquid, and pass through filtering and washing with deionized water.Repetitive operation 4 times.Thus, obtain toner cake.The toner cake obtaining is dry with vacuum drier.By the sieve screening with 45 μ m apertures for dry toner cake, thereby obtain toner-particle.Operation is subsequently to carry out with mode identical in toner production example 1, thus acquisition toner (TNR 101).

< toner is produced routine 4>

Except using compound (101) to (159) to replace the compound with azo skeleton structure (150) in toner production example 3, according to toner of the present invention (TNR 102) to (TNR 159) to obtain with mode identical in toner production example 3.

< toner is produced routine 5>

Except using the compound being represented by general formula (160) to (163) to replace respectively the compound being represented by formula (160) as colorant in toner production example 3, according to toner of the present invention (TNR160) to (TNR 163) to obtain with mode identical in toner production example 3.

< toner is produced routine 6>

Except using the compound with azo skeleton structure (150) in compound (107), (110), (119), (152) and (157) replacement toner production example 5, according to toner of the present invention (TNR 163) to (TNR 177) to obtain with mode identical in toner production example 5.

Comparative example 3

The benchmark that shows evaluation index is with toner and relatively being produced by following methods with toner according to toner of the present invention.

< benchmark is produced routine 2> with toner

Except not adding the compound with azo skeleton structure (150) in toner production example 3, toner for benchmark (TNR 178) is to obtain with mode identical in toner production example 3.

< benchmark is produced routine 3> with toner

Except not adding the compound with azo skeleton structure (150) in toner production example 5, toner for benchmark (TNR 179) to (TNR 181) is to obtain with mode identical in toner production example 5.

< relatively produces routine 2> with toner

Except using the comparative compound 1 of 1.8 parts to replace the compound with azo skeleton structure (150) in toner production example 3, relatively using toner (TNR 182) to obtain with mode identical in toner production example 3.

< relatively produces routine 3> with toner

Except using the comparative compound 1 of 1.8 parts to replace the compound with azo skeleton structure (150) in toner production example 5, relatively using toner (TNR 183) to (TNR 185) to obtain with mode identical in toner production example 5.

Embodiment 6

The toner obtaining in the present invention is according to following methods evaluation.

Use the above toner of producing, output image sample, and its image property of describing is subsequently compared and evaluated.Image property relatively in, logical paper long duration test is used LBP-5300[Canon Inc. to manufacture] transformation apparatus as image forming apparatus (hereinafter, being abbreviated as LBP), carry out.In when transformation, the developing blade in handle box (hereinafter, being called CRG) is by having 8[μ m] the SUS scraper plate of thickness replace.Carry out further transformation thus with respect to can the apply-200[V of development deviation being applied to as the developer roll of toner carrier] scraper plate bias voltage.

Use Coulter Multisizer[Beckman Coulter, Inc. manufactures], and the interface of the distribution of output number and volume distributed median [Nikkaki-Bios Co., Ltd. manufactures] and PC are connected to Coulter Multisizer.Sodium chloride is used for to electrolyte solution, and uses 1% NaCl aqueous solution.For example, can use ISOTON R-II[Beckman Coulter, Inc. manufactures].Concrete measuring process is at Beckman Coulter, shown in the catalogue (version in February, 2002) of Coulter Multisizer and the operation manual of measuring equipment that Inc. publishes.Process is as follows.

2 to 20mg measurement sample is added into 100 to 150ml electrolyte aqueous solution.Use ultrasonic dispersion machine to disperse about 1 to 3 minute the electrolyte solution with suspended sample.Use the aperture of the 100 μ m of Coulter Multisizer, measure volume and the number of the toner-particle with the particle diameter that is not less than 2.0 μ m and is not more than 64.0 μ m.Data allocations to 16 passage obtaining, and measure weight average particle diameter D4, number average bead diameter D1 and D4/D1.

The evaluation > of the colouring power of < toner

Under the environment of normal temperature and normal wet [N/N (23.5 ℃, 60%RH)], solid image is at transfer paper (75g/m ²paper) upper with 0.5mg/cm ²toner applied amount form.Use reflection of the concentration Spectrolino (Gretag Macbeth GmbH manufacture), measure the concentration of solid image.The colouring power of toner is evaluated by solid image color improvement rate.

Use the solid image color of toner (TNR 78) benchmark for as reference value, determine and use according to suspension polymerization by the improvement rate of the solid image color that uses the compound that represented by formula (160) and form as toner (TNR1) to (TNR 59) of colorant production.

Use the solid image color of toner (TNR 79) benchmark for as reference value, determine and use according to suspension polymerization by the improvement rate of the solid image color that uses the compound that represented by formula (161) and form as toner (TNR60), (TNR 63), (TNR 66), (TNR 69), (TNR 72) and (TNR 75) of colorant production.

Use the solid image color of toner (TNR 80) benchmark for as reference value, determine and use according to suspension polymerization by the improvement rate of the solid image color that uses the compound that represented by formula (162) and form as toner (TNR61), (TNR 64), (TNR 67), (TNR 70), (TNR 73) and (TNR 76) of colorant production.

Use the solid image color of toner (TNR 81) benchmark for as reference value, determine and use according to suspension polymerization by the improvement rate of the solid image color that uses the compound that represented by formula (163) and form as toner (TNR62), (TNR 65), (TNR 68), (TNR 71), (TNR 74) and (TNR 77) of colorant production.

Use the solid image color of toner (TNR 178) benchmark for as reference value, determine and use according to suspension comminution granulation by the improvement rate of the solid image color that uses the compound that represented by formula (160) and form as the toner (TNR 101) to (TNR 159) of colorant production.

Use the solid image color of toner (TNR 179) benchmark for as reference value, determine and use according to suspension comminution granulation by the improvement rate of the solid image color that uses the compound that represented by formula (161) and form as toner (TNR 160), (TNR 163), (TNR 166), (TNR 169), (TNR 172) and (TNR 175) of colorant production.

Use the solid image color of toner (TNR 180) benchmark for as reference value, determine and use according to suspension comminution granulation by the improvement rate of the solid image color that uses the compound that represented by formula (162) and form as toner (TNR 161), (TNR 164), (TNR 167), (TNR 170), (TNR 173) and (TNR 176) of colorant production.

Use the solid image color of toner (TNR 181) benchmark for as reference value, determine and use according to suspension comminution granulation by the improvement rate of the solid image color that uses the compound that represented by formula (163) and form as toner (TNR 162), (TNR 165), (TNR 168), (TNR 171), (TNR 174) and (TNR 177) of colorant production.

The evaluation criterion of the improvement rate of solid image color is below shown:

A: the improvement rate of solid image color is more than 20%

B: the improvement rate of solid image color is for being not less than 10% and be less than 20%

C: the improvement rate of solid image color is for being not less than 5% and be less than 10%

D: the improvement rate of solid image color is for being less than 5%

If the improvement rate of solid image color is more than 10%, judge that colouring power is good.

> is evaluated in hazing of < toner

At the environment of normal temperature and normal wet [N/N (23.5 ℃, 60%RH)], and under the environment of high temperature and high humidity [H/H (30 ℃, 80%RH)], carry out image output test, wherein use transfer paper (75g/m ²paper), the image with 2% coverage rate is printed on 10,000 transfer papers.In this test, when durable evaluation completes, output has the image of white part.The whiteness [reflectivity Ds (%)] of white portion in the print image of measuring from use " REFLECTMETER MODEL TC-6DS " [Tokyo Denshoku Co., Ltd. manufactures] and the poor concentration (%) [=Dr (%)-Ds (%)] that hazes of calculating between the whiteness [average reflectance Dr (%)] of transfer paper.Use concentration evaluation the hazing when durable evaluation completes of hazing.

A: be less than 1.0%

B: be not less than 1.0% and be less than 2.0%

C: be not less than 2.0% and be less than 3.0%

More than D:3.0%

If hazed, concentration is less than 3.0%, judges and suppresses fully to haze.

The evaluation > of < toner transfer efficiency

Under high temperature and high humidity [H/H (30 ℃, 80%RH)] environment, carry out image output test, wherein use transfer paper (75g/m ²paper), the image with 2% coverage rate is printed on 10,000 transfer papers.In this test, when durable evaluation completes, detect transfer efficiency.By solid image on drum with 0.65mg/cm ²toner applied amount develop, and be transferred to transfer paper (75g/m ²paper) upper, thus uncertain image obtained.Toning dosage from drum and the difference between the toning dosage on transfer paper are tried to achieve transfer efficiency (when the toning dosage on drum is transferred on transfer paper fully, transfer efficiency is 100%).

A: transfer efficiency is more than 95%

B: transfer efficiency is not less than 90% and be less than 95%

C: transfer efficiency is not less than 80% and be less than 90%

D: transfer efficiency is less than 80%

If transfer efficiency is more than 80%, judge that transfer efficiency is good.

Comparative example 4

Relatively using toner (TNR 82) to (TNR 85) and (TNR 182) in (TNR 185), by tone, haze and transfer efficiency calculates by method in the same manner as in Example 6.

In relatively using toner (TNR 82), use the solid image color of toner (TNR 78) for benchmark as reference value, determine the improvement rate of solid image color.

In relatively using toner (TNR 83), use the solid image color of toner (TNR 79) for benchmark as reference value, determine the improvement rate of solid image color.

Use the solid image color of toner (TNR 80) for benchmark as reference value, determine the improvement rate of the solid image color of relatively using toner (TNR 84).

Use the solid image color of toner (TNR 81) for benchmark as reference value, determine the improvement rate of the solid image color of relatively using toner (TNR 85).

Use the solid image color of toner (TNR 178) for benchmark as reference value, determine the improvement rate of the solid image color of relatively using toner (TNR 182).

Use the solid image color of toner (TNR 179) for benchmark as reference value, determine the improvement rate of the solid image color of relatively using toner (TNR 183).

Use the solid image color of toner (TNR 180) for benchmark as reference value, determine the improvement rate of the solid image color of relatively using toner (TNR 184).

Use the solid image color of toner (TNR 181) for benchmark as reference value, determine the improvement rate of the solid image color of relatively using toner (TNR 185).

By by suspension polymerization, produce according to the present invention toner evaluation result, benchmark with the evaluation result of toner and relatively by the evaluation result of toner shown in table 3-1 and table 3-2.

By by suspension comminution granulation, produce according to the present invention toner evaluation result, benchmark with the evaluation result of toner and relatively by the evaluation result of toner shown in table 4-1 and table 4-2.

The evaluation result of table 3-1 suspension polymerization toner

The evaluation result of the toner of table 3-2 suspension polymerization

The evaluation result of the toner of table 4-1 suspension granulation

The evaluation result of table 4-2 suspension granulation toner

Table 4-2 (Continued)

From table 2 apparently, the use of finding to have the compound of azo skeleton structure has improved the dispersiveness of the magenta pigment in resin glue.

From table 3-1, table 3-2, table 4-1 and table 4-2 apparently, the evaluation result that the compound with azo skeleton structure (tone, haze and transfer printing performance) aspect whole evaluations has had.Therefore, the use that discovery has the compound of azo skeleton structure has improved the dispersiveness of the magenta pigment in resin glue, thereby the magenta toner with good colouring power is provided.Therefore, find that the compound with azo skeleton structure has suppressed to haze, thereby the magenta toner with high transfer efficiency is provided.

Although described the present invention according to exemplary, should be understood that and the invention is not restricted to disclosed exemplary.Thereby the scope of following claim meets explanation the most widely and comprises all such modifications and the 26S Proteasome Structure and Function being equal to.

This application requires the rights and interests of the Japanese patent application No.2012-043076 of submission on February 29th, 2012, herein by reference to its integral body is introduced.

Claims

1. a magenta toner, it comprises toner-particle, and described in each, toner-particle comprises:

Resin glue;

The compound with part-structure and macromolecule position, described macromolecule position has monomeric unit, and described part-structure is bonded to described macromolecule position; With

As the magenta pigment of colorant,

Wherein said part-structure is represented by following formula (1):

Formula (1)

Wherein by R ₁, R ₂with Ar one of at least with linking group or singly bound to described macromolecule position;

Be not bonded to the R at described macromolecule position ₁be not bonded to the R at described macromolecule position ₂represent independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇group; The Ar that is not bonded to described macromolecule position represents aryl;

Be bonded to the R at described macromolecule position ₁with the R that is bonded to described macromolecule position ₂represent independently of one another from alkyl, phenyl, OR ₅group or NR ₆r ₇group is removed the divalent group of hydrogen atom; The Ar that is bonded to described macromolecule position represents to remove from aryl the divalent group of hydrogen atom; With

R ₅to R ₇represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl; With

Described monomeric unit is represented by following formula (2):

Formula (2)

R wherein ₃represent hydrogen atom or alkyl; With

R ₄represent phenyl, carboxyl, carboxylic acid ester groups or carboxylic acyloxy amido.

2. magenta toner according to claim 1, the part-structure wherein being represented by described formula (1) is represented by following formula (3):

Formula (3)

Wherein

R ₁and R ₂represent independently of one another alkyl, phenyl, OR ₅group or NR ₆r ₇group;

R ₈to R ₁₂represent independently of one another hydrogen atom, COOR ₁₃group or CONR ₁₄r ₁₅group;

R ₁₃to R ₁₅represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl; With

R ₁, R ₂, and R ₈to R ₁₂one of at least there is the connecting portion with described macromolecule position.

3. magenta toner according to claim 1 and 2, wherein in described formula (1), R ₂nR ₆r ₇group, R ₆hydrogen atom, and R ₇it is phenyl.

4. according to the magenta toner described in claims 1 to 3 any one, wherein in described formula (1), R ₂nR ₆r ₇group, R ₆hydrogen atom, and R ₇it is the phenyl having with the connecting portion at described macromolecule position.

5. according to the magenta toner described in claim 1 to 4 any one, wherein in described formula (1), replace Ar substituent be one of at least COOR ₁₃group or CONR ₁₄r ₁₅group, wherein R ₁₃to R ₁₅represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl.

6. according to the magenta toner described in claim 1 to 5 any one, the part-structure wherein being represented by described formula (1) is bonded to the macromolecule position with the monomeric unit being represented by described formula (2) via carboxylic acid ester bond or carboxylic acid amide key.

7. according to the magenta toner described in claim 1 to 6 any one, the part-structure wherein being represented by described formula (1) is represented by following formula (4):

Formula (4)

Wherein L represents to be connected to the divalent linker at the macromolecule position with the monomeric unit being represented by above formula (2).

8. according to the magenta toner described in claim 1 to 6 any one, the part-structure wherein being represented by described formula (1) is represented by following formula (5):

Formula (5)

Wherein

R ₁₄and R ₁₅represent independently of one another hydrogen atom, alkyl, phenyl or aralkyl; With

L represents to be connected to the divalent linker at the macromolecule position with the monomeric unit being represented by above formula (2).

9. according to the magenta toner described in claim 1 to 7 any one, wherein said magenta pigment is represented by following formula (6):

Formula (6)

R wherein ₁₆to R ₂₃represent independently of one another hydrogen atom, chlorine atom or methyl.

10. according to the magenta toner described in claim 1 to 7 any one, wherein said magenta pigment is represented by following formula (7):

Formula (7)

R wherein ₂₄to R ₃₄represent independently of one another hydrogen atom, chlorine atom, the tert-butyl group, cyano group or phenyl.

11. according to the magenta toner described in claim 1 to 10 any one, and wherein said toner-particle is used suspension polymerization or suspension comminution granulation to produce.